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This letter considers a multi-user wireless communication system employing physical network coding (PNC), where a pair of users communicates with each other via a relay. To attain reliable communication over time varying channels, we apply an opportunistic scheduling scheme for the PNC to both the broadcast channel phase and the multiple access channel phase. We propose two criteria for selecting users based on the channel norm and the minimum distance. Also, an efficient method to compute the minimum distance for superposed QPSK signals is introduced. Simulation results show that the proposed scheduling for PNC provides a significant improvement over conventional schemes.