I give full credit for the below information to Brookelizabeth who posted it in one of her TRs or PTRs. I'm not a stalker... I promise.

But I've been using the Microsoft One Note program that basically lets you take screen shots of things and file them away in an online notebook. It's been very handy for Disney planning. Anyway, here is her photopass info. I agree, the Captain Hook shot is very cute. Definitely a must-do!!
Photopass "Extras"
What: Tinker Bell - in your palm
Where: Magic Kingdom - On Main Street, USA or around the castle
Epcot - In front of Spaceship Earth
When: Most times
What: Captain Hook - sword fight
Where: Magic Kingdom - by Pirates of the Caribbean
When: Most times
What: Ghost - in a carriage
Where: Magic Kingdom - Haunted Mansion
When: Mornings (or when Disney's PhotoPass Photographer is there)
What: Baby Simba - in your arms
Where: Disney's Animal Kingdom - Discovery Island
When: Most Times
Who: Stitch - coming out of the ground
Where: Disney's Hollywood Studios - Hollywood and Sunset Boulevards
When: Most times
Who: Stitch - on a bench eating ice cream
Where: Magic Kingdom - Main Street, USA
Epcot
Disney's Hollywood Studios - Between 2-3pm only
When: Most times
Who: Mickey, Minnie and Goofy - in a hang glider
Where: Epcot - between the Fountain of Nation stage and World Showcase Plaza
When: Most times
Who: Mickey Mouse - on a bench with you
Where: Disney's Hollywood Studios
When: Between 2-3pm
Who: Minnie Mouse - on a bench with you
Where: Disney's Hollywood Studios
When: Between 2-3pm
Who: Lilo - taking a picture of you
Where: Disney's Hollywood Studios
When: Between 2-3pm