The six-polarization shift keying quadrature (6PolSK-QPSK) has been proved to be an alternative to four-dimensional (4D) modulation scheme. A variety of transmission compensation schemes have been developed for 24-Point 6PolSK-QPSK combining the advantages of polarization multiplexing quadrature phase shift keying (PM-QPSK) and polarization switched quadrature phase shift keying (PS-QPSK). In order to further improve the transmission rate of the signal system, 32-Point 6PolSK-QPSK signal modulation has been studied. We propose a novel encoding rule and compensation scheme for 32-Point 6PolSK-QPSK modulation by classifying symbols. The simulation tool based on VPItransmissionMaker10.1 is equipped with 32-Point 6PolSK-QPSK signal transmission system and the off-line digital signal processing (DSP) module is applied to MATLAB to prove the method proposed in this paper. The simulation results show that the error performance of 2.6 dB and 8.7 dB are improved for unrevised and revised data transmission, compared with the 32-Point 6PolSK-QPSK signal scheme obtained by rotating PM-QPSK.