The preparation of a facilitated transport membrane of polyurethane (PU) containing silver nanoparticles is reported. The propylene and propane sorption was investigated aiming at the selective separation from C3s mixtures. The silver particles were photogenerated in situ into the polyurethane matrix using UV light radiation and silver triflate (AgCF3SO3) as precursor. The morphological properties of these membranes (PUAg) reveled great dispersion of silver particles, which size was smaller than 110 nm. The propylene solubility in PUAg resulted more than four times superior to the one for the pure PU membrane, revealing the high affinity between silver and propylene. Flory–Huggins theory was more accurate to describe the propylene sorption behavior in PUAg than Henry's model. The ideal solubility selectivity of PUAg membrane resulted 24.4, indicating that there is a good potential for an industrial application aiming at the separation of propylene/propane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42916.