To date, investigations onto the regulation of reactants mass transfer has been paid much less attention in environmental catalysis. Herein, we demonstrated that by rationally designing the adsorption sites of multi-reactants, the pollutant destruction efficiency, product selectivity, reaction stability and secondary pollution have been all affected in the catalytic chlorobenzene oxidation (CBCO). Experimental results revealed that the co-adsorption of chlorobenzene (CB) and gaseous O2 at the oxygen vacancies of CeO2 led to remarkably high CO2 generation, owning to their short mass transfer distance on the catalyst surface, while their separated adsorptions at Br?nsted HZSM-5 and CeO2 vacancies resulted in a much lower CO2 generation, and produced significant polychlorinated byproducts in the off-gas. However, this separated adsorption model yielded superior long-term stability for the CeO2/HZSM-5 catalyst, owning to the protection of CeO2 oxygen vacancies from Cl poisoning by the preferential adsorption of CB on the Br?nsted acidic sites. This work unveils that design of environmental catalysts needs to consider both of the catalyst intrinsic property and reactant mass transfer; investigations of the latter could pave a new way for the development of highly efficient catalysts towards environmental pollution control.