Highly permeable pocket-shaped microfiltration membranes with binary porous structures, which are composed of brominated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO), were prepared on needles by breath figure (BF) and colloidal crystal template (CCT) methods. In colloidal crystal templates, the membrane pore size in the bottom layer was adjusted by SiO2 microsphere diameter in the colloidal crystal template, while that in the top layer was adjusted by changing the BPPO concentration. The permeability of the binary porous membrane prepared by BF and CCT methods was higher than that of membranes only prepared by the BF method. Due to high permeability and antifouling properties, the pocket shaped binary porous membrane was connected to a syringe and used as a filter film in microfiltration and sample preparation fields.