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We analyze the error performance of the physical-layer network coding (PNC) protocol without channel coding in bidirectional relay networks for binary phase shift keying (BPSK) over Rayleigh fading channels. It is assumed that a bidirectional relay network consists of two sources and a relay, where each node has a single antenna and operates in a half-duplex mode, and the PNC over finite GF(2) is employed. In this system, since the maximum-likelihood (ML) detection metric of the multiple access channel (MAC) at the relay is given by the sum of two exponential functions, it is not possible to utilize the classical Euclidean distance rule. To make the performance analysis tractable, we approximate the ML detection metric by adopting the max-log approximation. Then we derive tight upper and lower bounds in closed form for the average symbol error probability of the MAC at the relay. Finally, we obtain tight upper and lower bounds in closed form for the end-to-end average bit-error rate (BER).