Can Vitamin E boost nitric oxide? You bet it can! It doesn't directly raise nitric oxide levels like a Citrulline, Arginine or high nitrate foods However, there evidence clearly shows that in some men, especially those who need it, Vitamin E will do boost your NO levels.
Vitamin E is a powerful antioxidant and is known for the fact that it resides in lipids and thus provides protection where Vitamin C and virtually all other antioxidants cannot. For example, one set of researchers stated that "it is concluded that vitamin E, which is largely present as Î±-tocopherol, is the only significant lipid-soluble, chain-breaking type of antioxidant present in human blood." 
Before we gone, it should be pointed out that Vitamin E really isn't just one compound. Vitamin E is actually composed of four tocopherols: alpha, beta, gamma and delta and there are also four tocotrienols that are part of the Vitamin E complex as well. Some men swear that tocotrienols help with keeping the hair on your head for example. And gamma tocopherol plays a role in cardiovascular and prostate cancer protection. However, most Vitamin E supplements are still the "old school" alpha tocopherol form.
And realize that the alpha tocopherol form is provided for only one reason: to save money. However, you do NOT want in my opinion to take only the alpha form, because doing this can lower your gamma and delta tocopherol levels.  There is some research that even indicates this could put you at increased risk for prostate cancer, because the gamma form in particular plays a significant role there. Because of this, you always want to buy Vitamin E as mixed tocopherols (and ideally tocotrienols), even though it is generally more costly.
So how does Vitamin E raise nitric oxide levels? Here are a few key ways:
1. Increased eNOS Activity. Both gamma and alpha tocopherols increase nitric oxide synthase activity, the key enzyme involved in producing your precious nitric oxide.  Because of this, both of these increase nitric oxide generation. One study on hypertensive rats showed that Vitamin E lowered blood pressure at widely varying dosages of Î±-tocopherol. 
2. Free Radical Protection. One of the free radicals (peryoxynitrite) that your arteries have to deal with can actually slow down your nitric oxide production but by a different means:
"Oxidation of tetrahydrobiopterin by peroxynitrite in oxidant-stressed endothelium compromises nitric oxide synthase (eNOS) activity while amplifying superoxide production; this mechanism contributes prominently to the endothelial dysfunction that characterizes many common clinical disorders." 
Again, it's not alpha tocopherol, the most common Vitamin E supplement, that can help but rather gamma. Gamma mops up the damaging molecule and the above study notes that in men with high cholesterol, vasodilation has improved, which means in this case that nitric oxide and blood flow were increased.
3. Arteriosclerosis Protection. Vitamin E also may protect your endothelial nitric oxide by protecting your arteries from arteriosclerosis. How does it do this? Oxidized LDL, the "bad" cholesterol, is what lodges in the lining of the arteries and Vitamin E protects LDL from oxidizing in the first place.  And remember: arteries that are lined with plaque cannot produce nearly as much nitric oxide for you.
This brings up an important point: the man most likely to benefit from Vitamin E is someone with some kind of cardiovascular issue such as high blood pressure, erectile dysfunction and/or high cholesterol. A young buck may want to take some Vitamin E for protective purposes, but he is probably not going to be able to discern a noticeable difference.
And are there any human studies to show this? One study on mild hypertensive patients ("systolic blood pressure, SBP: 140-160 mmHg; diastolic blood pressure, DBP: 90-100 mmHg") found that Vitamin E dropped systolic blood pressure, diastolic blood pressure and pulse by 24%, 13% and 4.3%, respectively.  These are big drops for just one supplement to achieve. The decrease in systolic pressure is particularly impressive! These kinds of big drops usually come from big boosts in nitric oxide, which is just what we would expect.
CAUTION: If you are on any medications or have any medical conditions, please talk to your physician first before making any changes. Some supplements have interaction or unexpected actions. Also, one study showed increased in blood pressure in some diabetic patients. This was with a very large dose and alpha tocopherol only. 
Other cohorts that have shown big drops in blood pressure were kidney failure patients, who have very high blood pressure and dropped around 30 points mm systolic.  The rule seems to be that the higher your blood pressure, the bigger the correction.
A couple of final thoughts: some study work has shown that Vitamins C and E together can provide synergistic benefits.  Vitamin C is probably best taken in the "salt form", i.e. Emergen-C or Ester-C on an empty stomach. Note the conclusions of this in vitro study:
"Coincubation with ascorbic acid (100 Î¼M, 24 hr) amplified the effects of Î±-tocopherol on eNOS phosphorylation and NO formation, which is possibly related to the regeneration of oxidized Î±-tocopherol by ascorbate. Our data suggest that vasoprotective effects of Î±-tocopherol in vivo may be related to an increase of NO formation. The effect of Î±-tocopherol seems to be dependent on tissue saturation with ascorbic acid, and both vitamins may act synergistically to provide optimal conditions for endothelial NO formation." 
1) J Nutr, 2003 Oct, 133(10):3137-40, "Supplementation of diets with alpha-tocopherol reduces serum concentrations of gamma- and delta-tocopherol in humans"
2) Am J Clin Nutr, Dec 2001, 74(6):714-722, "Î³-Tocopherol, the major form of vitamin E in the US diet, deserves more attention"
4) Am J Hypertens, 1999, 12(8):839-844, "Î±-tocopherol increased nitric oxide synthase activity in blood vessels of spontaneously hypertensive rats"
5) Int J Vitam Nutr Res, 2002 Oct, 72(5):309-14, "Vitamin E can reduce blood pressure in mild hypertensives"
7) Hypertension, 2001, 38:606-611, "Antioxidant Effects of Vitamins C and E Are Associated With Altered Activation of Vascular NADPH Oxidase and Superoxide Dismutase in Stroke-Prone SHR"
8) Am J Cardiol, Jan 15 1998, 81(2):231-3, "Effects of increasing doses of alpha-tocopherol in providing protection of low-density lipoprotein from oxidation"
9) Journal of Hypertension, Jan 2007, 25(1):227-234, "The effect of vitamin E on blood pressure in individuals with type 2 diabetes: a randomized, double-blind, placebo-controlled trial"
10) Annals of the New York Academy of Sciences, Dec 2004, 1031:74â€“85, "Î±-Tocopherol and Endothelial Nitric Oxide Synthesis"