No, PlayOnLinux uses Wine. PlayOnLinux is literally just designed to give proper configuration values for particular proprietary programs people want to install.

Wine is just a Windows API compatibility layer; it's useful for running proprietary programs that aren't available for GNU/Linux, but it could also be used to run a libre program that uses the Windows API or DirectX, for example. Such libre programs do exist, although they are uncommon. One example is a program called "XM Solitaire", which has actually been ported to the OpenPandora using Wine:

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