1. Han has quite an interesting backstory, one where he is a member of the Imperial Navy before being drummed out for forming an unlikey bond with a Wookie named Chewbacca. This would make a very good first episode or beginning.
2. His backstory would be very interesting as you would learn about any love interests he may have had, and also a lot more about his smuggling days.
3. Finally, you'd be able to see if he actually made the Kessel Run in less than 12 Parsecs.