Permeability coefficients of hydrogen sulfide in fluorinated polymers are anomalously low when compared to its permeability in nonfluorinated polymers. As a result, fluoropolymer membranes have unusual selectivities for gas pairs involving H2S. For example, while the mixture CO2/H2S selectivity is 0.66 for nonfluorinated, rubbery poly( dimethylsiloxane), this selectivity is 8.0 for a fluoroelastomer composed of tetrafluoroethylene, perfluoromethyl vinyl ether, and perfluoro-8-cyano-5-methyl-3,6-dioxa-1-octene (TFE/PMVE/ 8CNVE) and 27 for a glassy, cyclic perfluoroether (Cytop) under similar test conditions. The low H2S permeability in fluoropolymers is caused primarily by unexpectedly low H2S solubility in the fluorinated polymer matrices. For instance, H2S solubility in a Teflon AF copolymer of tetrafluoroethylene and 2,2-bis(trifluoromethyl)-4,5difluoro-1,3-dioxole is approximately 5 times lower than the value predicted by a correlation of solubility with gas critical temperature. This low solubility is not related to penetrant size or condensability effects but rather is caused by unfavorable molecular interactions between H2S and fluoropolymers. As a result of this unusual solubility behavior, fluorinated glassy polymers are more resistant to H2S-induced plasticization than nonfluorinated glasses. These findings may prove useful in emerging membrane applications that involve H2S, such as natural gas treatment.