Carmen Sandiego, especially the USA and World CD-ROM games from Borderbunds for PC in the mid-90s, cause they featured the Chief from the game show.
But I also have to mention the Videosmarts Teaching Teddy series. It was a VCR game with it's own controller to teach kids basic things like the alphabet, colors, shapes, all stuff you find on Sesame Street.
Microworlds on mid-90′s Macintosh's. It was a GUI for teaching LOGO that I remember using from 2nd grade through 5th grade. I seem to remember at least 2 versions of that game in use. The earlier version was relatively basic, but by 4th and 5th grade we were using an advanced version that allowed for animation, audio playback, and even let us make presentations easily and having fun doing it.
Microworlds constituted my first programming experience, and I loved it! I recall making complex subroutines for drawing objects on screen, but the last time they let us do that was probably 3rd grade, and most kids thought it was kinda boring.