rgb(255,255,255)
notation has been available since CSS1. But #ffffff
seems to be vastly more popular.
Obviously it's slightly more compact. I know that hex is more closely related to the underlying bytes, and understand that there would be advantages in carrying out arithmetic on those values, but this isn't something you're going to do with CSS.
Colour values tend to be originated by designers (such as myself) who would never encounter hex notation anywhere else, and are much more familiar with the decimal notation which is the main way of specifying colour in the apps they use -- in fact I have met quite a few who don't realise how a given hex value breaks down into RGB components and assumed it didn't directly relate to the colour at all, like a Pantone colour system reference (eg PMS432).
So, any reason not to use decimal?
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.