Well, if you look closely at pictures that show the DVI outputs of video cards, you will notice that they use DVI-I. This means that via one output they send out a digital signal as well as an analog. When you use a DVI to VGA adapter, you are actually only taking an existing signal putting it on a different pinout and connector.
There will be no quality difference.
EDIT: I see that Alvin beat me to it by seconds. Meh, we said the same thing anyways