If we need to acess oll the values in the PeopleEditor control, we can iterate through the entities present in PeopleEditor:
Suppose we have a PeopleEditor control PE1 so the code will be :
ArrayList entities = PE1.ResolvedEntities;
foreach (object entity in entities)
PickerEntity pickerEntity = (PickerEntity)entity;
string accountName = pickerEntity.Key;
string displayName = pickerEntity.DisplayText;
// pickerEntity.EntityDate has other values like first name, last name, etc you might be interested in.