rgb(255,255,255) notation has been available since CSS1. But #ffffff seems to be vastly more popular.
rgb(255,255,255)
#ffffff
Obviously it\'s slightly more compact
Hex values are easier to copy and paste from your favourite image editor.
RGB values are easier to manipulate with Javascript.
(My favourite Hex colour value is #EDEDED and a site we made for a client involved in motorsport had a background colour of #F1F1F1 :-)
Ed.