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Rurouni Kenshin: Meiji Kenkaku Romantan
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Meteor Methuselah
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Rurouni Kenshin and Immortal Rain both begin with the female deuteragonist attacking the eponymous character. Kaoru and Machika learn later on who they really are and gradually fall in love with them.
Kenshin and Rain are usually easy-going, goofy, clumsy, and very, very kind, but will become serious and ready to defend those important to them.
Both have a dark past and enemies who they must confront if it means living peacefully with those who have become like a family to them.