Polyethylene glycol (PEG) is an important additive that can effectively improve the desulfurization performance of polyurethane membranes for fluid catalytic cracking (FCC) gasoline via pervaporation (PV). Polyurethane membranes were characterized using Fourier transform infrared spectroscopy (FT-IR) analysis and X-ray diffraction techniques. Permeation vaporization experiments were carried out for sulfur-containing compounds in FCC gasoline using homemade polyvinylidene fluoride (PVDF) bottom membranes. Compared with the traditional osmogasification membrane, the PEG/polyurethane (PU) hybrid membrane shows a higher sulfur enrichment factor (6.00) and permeation flux (2.20 kg/(m(2).h)), which confirms the superior performance of the proposed PU membrane. Through the analysis of meteorological chromatography, it can be clearly observed that the PEG/PU membrane can effectively remove the thiophene and its derivatives in FCC gasoline.