If you have an animal lover in your home, CardLine Animals from Asmodee is a great way to learn defining characteristics of a variety of species, while playing a game. The mathematical uses are plentiful too!
Ghost Fightin' Treasure Hunters! is an enjoyable co-operative game that's great for family game night, and pretty much any other time you can play a game. The large amount of playing pieces help encourage the youngest of players to join in.