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Now for the answers. Little graphic (icons representing the choices), and the list. In addition to the top ten episodes, I also put the remainder of the episodes in order of favoritism too.
I based the picks for characters and duos on how much enjoyment I get every time they're onscreen. For instance, as much as I adore the Damon/Stefan relationship, there are definitely times when I get frustrated with how Damon is the loser-boy in relation to Stefan, whereas there is not one moment that Stefan and Caroline are on screen that I'm not a puddle of squee and/or goo. With characters, Stefan dropped off the top five (for the first time) because I included non-main characters, and as much as I do love him, the Stefan we saw in "The Dinner Party" irritated me so much, and that is something that numbers four and five have never done.
** 10 Favorite Characters **
01.) Damon Salvatore
02.) Elena Gilbert
03.) Caroline Forbes
04.) Elijah
05.) Katherine Pierce
06.) Stefan Salvatore
07.) Alaric Saltzman
08.) Bonnie Bennett
09.) Jeremy Gilbert
10.) Sheriff Liz Forbes

** 10 Favorite Duos **
01.) Damon and Elena
02.) Stefan and Caroline
03.) Damon and Stefan (non-romantic)
04.) Damon and Alaric (non-romantic)
05.) Elijah and Katherine
06.) Jeremy and Bonnie
07.) Stefan and Katherine
08.) Damon and Liz (non-romantic)
09.) Elena and Caroline (non-romantic)
10.) Damon and Katherine (non-romantic)

** 10 Favorite Episodes **
01.) S01.19 - Miss Mystic Falls
02.) S02.01 - The Return
03.) S02.21 - The Sun Also Rises
04.) S01.14 - Fool Me Once
05.) S01.17 - Let the Right One In
06.) S02.22 - As I Lay Dying
07.) S02.07 - Masquerade
08.) S02.16 - The House Guest
09.) S02.10 - The Sacrifice
10.) S01.13 - Children of the Damned

**The Rest ... **
11.) S01.21 - Isobel
12.) S01.18 - Under Control
13.) S02.13 - Daddy Issues
14.) S02.05 - Kill or Be Killed
15.) S02.09 - Katerina
16.) S01.07 - Haunted
17.) S02.18 - The Last Dance
18.) S01.22 - Founder's Day
19.) S02.06 - Plan B
20.) S02.17 - Know Thy Enemy
21.) S02.11 - By the Light of the Moon
22.) S01.11 - Bloodlines
23.) S01.12 - Unpleasantville
24.) S01.06 - Lost Girls
25.) S01.15 - A Few Good Men
26.) S02.04 - Memory Lane
27.) S01.04 - Family Ties
28.) S01.20 - Blood Brothers
29.) S02.02 - Brave New World
30.) S02.19 - Klaus
31.) S01.09 - History Repeating
32.) S01.10 - The Turning Point
33.) S02.03 - Bad Moon Rising
34.) S02.08 - Rose
35.) S01.05 - You're Undead to Me
36.) S01.08 - 162 Candles
37.) S02.12 - The Descent
38.) S02.15 - Dinner Party
39.) S02.20 - The Last Day
40.) S01.16 - There Goes the Neighborhood
41.) S02.14 - Crying Wolf
42.) S01.03 - Friday Night Bites
43.) S01.02 - The Night of the Comet
44.) S01.01 - Pilot