Yukino and Soichiro - Kare Kano
Tsubasa and Kazuma - Kare Kano
Tsubaki and Takefumi - Kare Kano
Miyako and Hiroyuki - Kare Kano
Nagisa and Tomoya - Clannad
Kyoko and Ren - Skip Beat!
Tohru and Kyo - Fruits Basket
Misaki and Usui - Maid-sama!
Karin and Usui - Karin
Kaname and Sousuke - Full Metal Panic!
Shana and yuuji - Shakugan no Shana
Haruka and Yuuto - Nogizaka Haruka no Himitsu
Haruhi and Tamaki - Ouran High School Host Club
Melfina and Gene - Outlaw Star
Yumi and Sachiko - Maria Watches Over Us
Relena and Heero - Gundam Wing
I could've kept going, but I think there is a good place to stop for now, plus I wanted to avoid some of the more spoilers! ones. I also should be working since I am at work
Finally, I notice you include Ash and Misty, which begs the question: What level of http://en.wikipedia.org/wiki/Shipping_%28fandom%29 is needed for an unofficial couple to be a couple?