There's not a lot of Mal/Kaylee out there, really, but it seems to be increasing. Your best place to start is iluvmycaptain. There's lots of good stuff linked from there. I'd specifically recommend "In Small Degrees (Everybody Falls)" (http://musesfool.livejournal.com/995997.html#cutid1) by musesfool, and anything else by her, as well as "Count the Ways" (http://pixeldimensia.livejournal.com/12353.html#cutid1) by pixeldimensia.
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There's not a lot of Mal/Kaylee out there, really, but it seems to be increasing. Your best place to start is
Hope you enjoy!