It should work but I haven't done it on a card that had one vga and only one dvi connector. You will need one adapter. A card with two dvi connectors will support two vga monitors via two adapters just fine.
Again, this is not how it normally works. there has to be digital to analog circuitry to get the signal out on the DVI analog pins, and because of the extra components most manufacturers only provide analog out on one of the DVI ports. it can vary depending on the card/manufacturer/version though.