alcohol is a vasodilator at lower doses but at higher doses it acts as a vasocontrictor. (1)
caffeine is a vasoconstrictor. hence the help you receive from drinking coffee with aspirin after getting a headache related to drinking alcohol.
(1) - http://www.scientificamerican.com/article.cfm?id=what-are-the-effects-of-a
As a general guideline, most stimulants will act as vasoconstrictors and most depressants will act as vasodilators. There are obvious exceptions to this rule (such as NO2)
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No, actually caffeine is a vaso-constrictor, yet at the same time is a vasodiolator to the lungs. In short it is not a vaso-diolator for the primary blood vessels!