The hydration of cyclohexene was determined in a stirred tank of 100 mL in a batch mode in the presence of modified or unmodified resin as catalyst. The ion-exchange sulfonate resin was modified with alkyl secondary amine. At an optimum amination rate of 15%, the conversion of cyclohexene reached to 22% and the selectivity of cyclohexanol was 95.6%. In a temperature range of 90–150 °C, the activity and selectivity of the modified resin catalyst were much higher than those of the unmodified resin catalyst, which was attributed to the inclusion formed between cyclohexene and alkyl chain and also the quasi-lipophilic phase formed around the outer surface of resin beads. The formed quasi-lipophilic phase formed enhanced the conversion of cyclohexene and depressed the formation of by-products.