Membrane separation technology is widely used in water treatment. In this paper, we prepared polyphenylene sulfide/porous carbon nanofibers (PPS/PCNF) hybrid membranes by adding PCNF into PPS membranes. In the thermally induced phase separation (TIPS) process, PCNF could migrate to the top surfaces of the hybrid membranes, which made the pore size on the top surfaces of the membranes significantly decreasing and the pore size distribution became narrower. Compared with the conventional surface coating modified membranes, the surface coating material of PCNF would not falling off from PPS membrane, and it made the hybrid membranes to become more hydrophobic and to have the higher breaking elongation. PCNF, as a kind of heterogeneous nucleating agent, increased the melting temperature and the crystallization temperature of PPS/PCNF membrane, which resulted in PPS/PCNF membrane having the higher breaking elongation. Most importantly, PPS/PCNF hybrid membranes had a good intercepting performance, with bovine serum protein (BSA) intercepting rate of 92.7% and dye methylene blue (MLB) intercepting rate of 99.9%. Meanwhile, they also had a good removal effect on bacteria in strong polar organic solvent, and the removal rate achieved 93.7%. Thus, the PCNF hybridized PPS can play a crucial role on wastewater treatment in the future.