A novel reactive distillation (RD) process for phenol production with high energy efficiency was developed, in which concentrating cumene hydroperoxide (CHP) was integrated with its decomposition in the RD column using a cation exchange resin as the catalyst. Results from the kinetic experiments showed that the dry resin (AMBERLYST 35DRY) is superior to the wet one (AMBERLYST 35WET) because of the negative influence of the high water content in the latter. Meanwhile, the intrinsic kinetics of CHP decomposition catalyzed by the dry resin was obtained by regression analysis with consideration of diffusion resistances of the catalyst. A lab-scale RD column was designed by some calculations with the obtained kinetics, and the corresponding experiments were carried out to study the technical feasibility and the performance in terms of energy efficiency. Besides the high conversion and selectivity of the new RD process, results also showed obvious significance of utilizing the decomposition heat for the distillation separation.