It would be nice to see a log and a video example of the problem, but my guess is that you are using Monitor capture to capture the game, and the game is being played in Fullscreen mode. Monitor capture and Window capture can't be used to capture fullscreen games. You have to play them in Windowed or Borderless Windowed mode.
But a better solution would be to have 2 scenes: one with Window capture of the PVP.net client and one with Game capture of the actual LoL game, and use the Simple Scene Switcher to swap back and forth between them viewtopic.php?f=11&t=1785
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