The ones in bold are the ones that were correctly guessed.
1. NCIS (2) - Gibbs and Ducky
2. The Man From U.N.C.L.E. - Illya Kuryakin
3. Sapphire and Steel - Steel
4. The Professionals - Ray Doyle
5. Due South - Ray Vecchio
6. The Sandbaggers - Neil Burnside
7. Star Trek (TOS) - Spock
8. Star Trek (TNG) - Captain Piccard
9. Star Trek (DS9) - Julian Bashir
10. M*A*S*H - Hawkeye
11. Buffy The Vampire Slayer - Giles
12. Angel The Series - Wesley
13. Stargate SG-1 - Jack O'Neill
14. Babylon 5 - Michael Gariboldi
15. Grey's Anatomy - Ensemble cast
16. House (2) - House and Wilson
17. Starsky & Hutch - Ken Hutchinson
18. Sherlock Holmes - Sherlock Holmes
19. Raffles - A.J. Raffles
20. New Tricks - Ensemble cast