The mixture of acetophenone (AP) and 1-phenylethanol (PE), usually produced in petrochemical and biochemical processes, are difficult to be separated by the traditional distillation, crystallization, etc. It is of great significance to separate AP and PE by physical adsorption. A kind of b-cyclodextrin-cellulose based hypercrosslinked microspheres (HCCM) was prepared and used to adsorb and separate AP/PE. The structure of HCCM was characterized by FT-IR, N₂ adsorption desorption, scanning electron microscopy and transmission electron microscopy. The results showed that HCCM was a biomass based polymer microsphere with hierarchically porous structure formed by interweaving a large number of sugar units and phenyl rich units. The performance of HCCM for the adsorption and separation of AP/PE was studied. It was found that the equilibrium could be reached quickly, and the adsorption capacity of AP was higher than that of PE. Furthermore, PE, broke through much earlier than AP, with a long breakthrough interval and a high separation factor, which indicate that HCCM can separate AP and PE effectively. The recycling experiment proved that the material possessed excellent reusability.