A highly permeable brominated poly(phenylene oxide) (BPPO) microfiltration membrane with binary porous structures was fabricated by combination of the breath figure and colloidal crystal template methods. The pore size in the bottom layer of the membrane was adjusted by the diameter of SiO2 microspheres in the colloidal crystal template, while the pore size in the top layer of the membrane was adjusted by varying the BPPO concentration in the casting solution. The permeability of the membrane cast on the colloidal crystal substrate was much higher than that of the membrane cast on a bare silicon wafer. The binary porous BPPO membrane with high permeability and antifouling property was used for microfiltration applications. (C) 2015 Elsevier Inc. All rights reserved.