The water retained inside the sludge flocs is the bottleneck for the dehydration of sewage sludge, which hindered the following treatment. In this study, corn core powder was modified (MCCP) using sodium hydroxide (NaOH) and cationic surfactant cetyltrimethylammonium bromide (CTMAB) to break the structure of extracellular polymeric substances (EPS) and cell membrane for enhancing the dewaterability of sewage sludge. The dewatering performance, the properties of the treated sludge, the composition and distribution of EPS were investigated to discuss the dewatering mechanism of sludge. Adding 20% DS (mass of dry solids in sludge) of MCCP reduced the moisture content (MC) and the specific resistance of filtration (SRF) of the sludge by 40% and 55%, respectively. Then, correlation analyses were performed between dewatering indices of sludge and sludge properties. A multiple linear regression model was established which indicated the relationship between MC and the key factors reflecting sludge dewaterability, demonstrating that larger particle size of sludge flocs and more total dissolved solids in filtrate may be propitious to reduce content of bound water in sludge.