Sulfur dioxide (SO2) is the major air pollutant which is emitted from the power plant. In this study, hollow fiber membrane (HFM) separation process is applied for the improvement of SO2 removal efficiency in the post-combustion gas. HFM was produced by dry/wet phase inversion method and then coated with Polydimethylsiloxane (PDMS). The membrane morphology and characterization were examined with help of scanning electron microscope (SEM), energy dispersion of X-ray spectroscopy (EDX), Fourier transform infrared (FT-IR) and atomic force microscopy (AFM). Polyethersulfone (PES) hollow fiber membranes were tested for the SO2/N2 binary mixed gas separation. Single gas permeance of SO2, N2, and binary mixture gas (200 ppm of SO2) separation experiment was initiated to observe membrane behavior according to temperature and pressure difference and retentate flow rate. As a result, permeance of SO2 was 24.9–47.4 GPU and selectivity of SO2/N2 was 1.6–4.2. From the mixture gas separation experiment, SO2 removal efficiency increased according to stage cut and operating pressure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39711.