Hmmmm I think the idea of most beautiful woman is something that is interesting but Vanity Fair has seemingly gone about it in a very dim way. Beauty is a very compelling subject - lets be honest for a moment, we wouldn't have websites like tFS if we weren't all in some way interested in beauty, it's surrounding culture and people who are deemed beautiful. I don't think there is anything wrong with the idea of a magazine talking about female beauty in terms of saying such and such actress / model / personality has a face that is indicative of the current cultural perceptions of what is attractive.
However, the problem with the VF list is that it's very middle of the road and almost predictable. You have your completely obvious choices, a few out of touch additions that reek of tokenism and a couple of very bandwagony oh so trendy picks. What would have been more interesting would be if you get an eclectic group of people to talk about what beauty means to them / whose beauty inspires them. Get Woody Allen to wax poetic about Scarlett's allure or have Nicolas Ghesquiere say what makes girls like Jennifer Connelly or Hilary Rhoda so special to him. Get Zadie Smith in to do an essay, have someone who isn't Annie Liebowitz shoot a portfolio of great beauties throughout the ages.
Just do something that isn't Gisele with Testino for the ten millionth time. Angelina for the billionth time. Halle for the zillionth. Are these the only women worth talking about when it comes to phyiscal attractiveness?
The contents better blow the tired Helen of Troy concept out of the water. Ranking beauty is boring, talking about beauty can be compelling. Quite frankly I'd rather see a bit of attention payed to unconventional beauties, those on the list so far are all very very traditional - completely unchallenging in a way...