Pocahontas is voiced by Irene Bedard, but they brought in Broadway powerhouse Judy Kuhn to do her singing. Oddly averted with Mel Gibson, who was a much bigger star, and did his own singing, contrary to what you might expect.
Chief Powhatan and Keketa, whose speaking voices are done by Russell Means and Gordon Tootoosis, respectively, BOTH have their singing done by Jim Cummings!
Talking to Himself: David Ogden Stiers voiced both Radcliffe and Wiggins. Thus, in the numerous scenes between the two, Stiers is doing all the voice work.
The animal characters were meant to talk but were made mute in order to give the film a more "serious" tone.
Prior to his death in 1994, comedian JohnCandy recorded a good deal of dialogue for a talking turkey character named Redfeather. Alas, the character was cut, not only after Candy's death, but also after the aforementioned decision to keep the animals mute was made.
In the July 1995 issue of Disney Adventures magazine which promoted the movie, there's a behind-the-scenes section of pages that includes an early title card from pre-production. It features an early version of Disney's Pocahontas who looks much like Disney's Tiger Lily, with her eyes closed, head held up high, arms folded and surrounded by a few forest animals. This gives the implication that Tiger Lily might have been in consideration to be brought back, but under a different name and to fill in the eponymous role at one point.
Governor Ratcliffe was originally going to be voiced by Richard White (who previously voiced Gaston), but he was replaced by David Ogden Stiers (who had played Cogsworth in the same film) because the filmmakers felt that audiences would only think of Gaston whenever Ratcliffe spoke if White did the voice.