Novel molecularly imprinted polystyrene nanospheres composite alumina membranes (MIPS/CAM) were prepared by modifying the alumina membranes with MIPS nanospheres via microemulsion polymerization method. The as-prepared MIPS/CAM were characterized by Raman spectra, SEM, and UV vis techniques. The particle sizes of MIPS nanospheres ranging from 25.3 to 112.5 nm over MIPS/CAM could be tuned by controlling the surfactant amount and the adding rate of oil phase into water phase. The flux study showed that the MIPS/CAM possessed good porosity. The selective recognition of phenol over MIPS/CAM was much higher than that over the NIPS/CAM. The phenol adsorption amount and the selectivity coefficients of MIPS/CAM to phenol ( sephenol/SA) increased with decreasing the particle sizes of MIPS nanospheres. The MIPS/CAIVI showed good recovery performance of phenol from industrial SA effluent. (C) 2015 Elsevier B.V. All rights reserved.