One look at the Chief and one is bound to be intimidated. This can be because the Chief is in a bad mood, or if his daughter is in danger, but deep down he is extremely kind and rather sweet. He often looks stern and has never been seen smiling.
In the movie, when John, Michael, and the Lost Boys are out hunting Natives, they are captured by them instead and taken to the Native Camp and brought to the attention of the Chief, who thinks they've kidnapped his daughter Tiger Lily (who was actually kidnapped by Captain Hook) and he orders that the Boys will be burned at the stake if Tiger Lily doesn't return home by sunset. Luckily, Peter Pan saved Tiger Lily and the Chief set the Boys free and made them Honorary-Natives too and Peter the chief Little Flying Eagle. He also explained through the song What Made the Red Man Red? how the Red Man becomes red by falling in love with a maiden, to which Peter falls in love with Tiger Lily causing Wendy to become jealous and upset.
For some unknown reason, the Chief didn't appear in the sequel, Return to Neverland. But the most likely presumption is due to racial sensibilities.
The Indian Chief with the Indians in Peter Pan's Flight