With an iterative algorithm embedded into Aspen Plus and considering the effects of catalyst volume fraction and catalyst effectiveness, the reactive distillation (RD) process for direct hydration of cyclohexene to cyclohexanol is simulated and evaluated. Results indicate that the RD process, compared with the traditional reaction separation process, is infeasible in light of total annual cost (TAC) though it is theoretically reasonable from a previous study. The infeasibility of the RD process is found to be mainly due to the low catalyst effectiveness, rather than the slow reaction rate or limitation of catalyst loading in the RD column. Accordingly, a side reactor configuration (SRC) for the direct hydration of cyclohexene is proposed and evaluated. Results show the advantages of the SRC with fewer reactors and reveal that the TAC of the SRC with a single side reactor as the best choice for the direct hydration process reduces 11.41% of that of the traditional reaction separation process.