I don't think that color photography was invented until the early 1900s. Whether or not someone may have painted a picture of Vance is another issue, that's something that might be found in one of the museums that house collections of the Vance family. Most of the pictures I've seen of him were taken in his later years when his hair was gray or white. In looking through some of the trees on Ancestry, I see a couple of color portraits, though. If you have Ancestry, here are a couple of links:
http://trees.ancestry.com/tree/42224725/person/19749265896/photo/c3a74b88-421f-44e5-8d2e-9c1f062b3d14?src=search

http://trees.ancestry.com/tree/42224725/person/19749265896/photo/6223074d-3ef9-469e-8368-25605829e2fc?src=search

This 2nd one says "Confederate Colonels", which pictures 3 officers in uniform, all with dark hair. Zeb Vance has a long black beard and very black hair.

I hope you have Ancestry.

Deloris