I'm gonna cheat on your questions and just list my 10 favorites alphabetically. And for TV releases, I just named whatever sets came out this year instead of choosing a specific set.
The Devil's Rejects
Lost: Season One
Seinfeld: Season Four/Season Five/Season Six
The Simpsons: Season Six/Season Seven
Star Wars: Episode III- Revenge Of The Sith
Titanic (1997)
24: Season Four
The Twilight Zone: Season Two/Season Three/Season Four/Season Five (OK, I haven't seen S5 yet but it's a safe bet to be good

)
Undeclared: Season One
The Val Lewton Collection (Cat People/The Curse Of Cat People, I Walked With A Zombie/The Body Snatcher, Isle Of The Dead/Bedlam, The Leopard Man/The Ghost Ship, The 7th Victim/Shadows In The Dark: The Val Lewton Legacy)
And in the category of "It ain't a great DVD but I'm just happy that it's on DVD":
Alfred Hitchcock Presents: Season One
Kolchak: The Night Stalker: Season One
Millennium: Season Two/Season Three
Tales From The Crypt: Season One/Season Two
And my biggest hope for 2006 is Twin Peaks: Season Two.