Charged porous polymer membranes (CPMs) emerging as a multifunctional platform for diverse applications in chemistry, materials science and biomedicine have been attracting widespread attention. Fabrication of CPMs in a controllable manner is of particular significance for optimizing their function and maximizing practical values. Herein, we report the fabrication of CPMs exclusively from poly(ionic liquid)s (PILs), and their pore size and wettability were precisely tailored by rational choice of counter-anions. Specifically, a stepwise subtle increase in hydrophobicity of the counter-anions by extending the length of fluorinated alkyl substituents, i.e. from bis(trifluoromethane sulfonyl)imide to bis(pentafluoroethane sulfonyl)imide and bis(heptafluoropropane sulfonyl)imide, decreased the average pore size gradually from 1546 to 157 and 77 nm, respectively. Meanwhile, the corresponding water contact angles increased from 90 degrees to 102 degrees and 120 degrees. The sensitive control over the porous architectures and surface wettability of CPMs by systematic variation of anion hydrophobicity provides solid proof of the impact of PIL anions on CPM structure.