A new log-likelihood ratio (LLR) message estimation method is proposed for polarization-division multiplexing eight quadrature amplitude modulation (PDM-8QAM) bit-interleaved coded modulation (BICM) optical communication system. The formulation of the posterior probability is theoretically analyzed, and the way to reduce the pre-decoding bit error rate (BER) of the low density parity check (LDPC) decoder for PDM-8QAM constellations is presented. Simulation results show that it outperforms the traditional scheme, i.e., the new post-decoding BER is decreased down to 50% of that of the traditional post-decoding algorithm.