We don't have a TV and we also started showing our boys movies when they were 5 and 8. Here are some that have gone over well. As you can see, we're big on the older stuff. (I detest Disney and Pixar animated movies and pretty much anything made these days for kids because of the potty humor and nudge-nudge humor aimed at adults. Miyazaki is the big exception).
Kiki's Delivery Service
My Neighbor Totoro
Sprited Away
Singin' in the Rain
Bedknobs and Broomsticks
Candleshoe
Escape to Witch Mountain
Mary Poppins
Sound of Music
Adventures of Robin Hood w/Errol Flynn (warning - death by arrow)
Benji
Apple Dumpling Gang
The Parent Trap
My Friend Flicka
Wizard of Oz
The Secret Garden (we'd already read the book)
Nim's Island
Cool Runnings
E.T.
The Court Jester
Lassie Come Home
Swiss Family Robinson