Kim Possible (2002-2007, Disney). All episodes in chronological order from the wiki.
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I have to say that until i make this video series i had never noticed how important Drakken and Shego were to the development of Kim and Ron relationship, they played a key part in bringing them together. And in return, Kim and Ron played a key role in the development of Drakken and Shego relationship, and specially, a key role in Shego character development were she becomes a little less evil by the end of Season 4.

Drakken and Shego becoming a couple at the finale was never planned. It is something that both the creators and the director agreed to at the last possible moment. My theory is that they were leaving options for possible spin-offs, Tim/Jim, Hanna, all the couples they made, like Bonnie and Sr. Jr. and even Felix and Zita... i think one of spin-offs could have involved Kim/Ron and Shego/Drakken kids.