I doubt there's a way at the moment. You can only keep on top the movie window and the control window (BSplayer menu -> Options -> "Always on top" and "Always on top - control window"), but not the playlist one.
The only way to keep it on top, is to use an external application which can assign different windows behaviors, or to add a request into the Feature request section and keep finger crossed to make it available in next BSplayer releases
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