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:
http://repo.openpandora.org/?page=detail&app=xmsol-ptitseb
