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Physical layer network coding (PNC), where relay node is allowed to process the superimposed signal directly, can improve the network throughput and spectral efficiency greatly. In this paper, we extent nearest neighbor approximation to investigate the symbol error rate (SER) of PNC over AWGN channels. SER for BPSK and QPSK modulation is derived, and an algorithm is designed to calculate the SER for high order modulations. Simulation results validate the derived SER expressions can characterize the SER performance of PNC over AWGN channels.