The word "chocolate" is referring to the fact that these people look like they belong in a Willy-Wonka factory and/or lifestyle. They resemble the personification of a chocolate bar; if perhaps this person ate so much fudge, it is leaking through their every pore.
b) "Did you see that guy over there?" "Yeah, he is so chocolatey!" "He has a wicked chocolate face!!"
c) "I went to the all you can eat buffet today, and there was a guy with a chocolate face in the next booth."
d) John Candy.
e) John Goodman.
f) Meatloaf. The singer.