Wastewater containing volatile organic compounds (VOCs) is generated in various industrial processes and is seriously harmful to the natural environment and human health. Its treatment has become extremely important due to increasing environment concerns. Here, a high permeable membrane for fast and high-efficient VOCs removal from aqueous solutions by pervaporation is reported. The as-prepared PIM-1 membrane allows ultrafast permeation of VOCs and exhibits excellent VOCs selectivity, particularly for ethyl acetate, dimethyl ether, and acetonitrile. Typically, the PIM-1 membrane exhibits an ultrahigh flux and separation factor of 39.5 kg m m(-2) h(-1) and 189, respectively, in the pervaporation of 1.0 mol% aqueous ethyl acetate solution. Furthermore, the solubility-diffusion mechanism is revealed in the pervaporation of 10 kinds of 1.0 mol% VOCs solutions. It is found that the pervaporation performance is affected directly by physicochemical properties of VOCs. Moreover, effects of feed composition and temperature on the pervaporation are studied in details. (c) 2015 American Institute of Chemical Engineers AIChE J, 62: 842-851, 2016