Luminescent oligomers and polymers doped with silver(I) salts were used as optical sensors for ethylene and other gaseous small molecules. Films of poly(vinylphenylketone) (PVPK) or 1,4-bis(methylstyryl)benzene (BMSB) impregnated with AgBF(4), AgSbF(6), or AgB(C(6)F(5))(4) respond to ethylene exposures with a reversible emission quenching that is proportional to the pressure of the gas. Experiments with various analytes revealed that only gases capable of forming coordinate bonds with Ag(I) ions (i.e., ethylene, propylene, and ammonia) produced a sensing response. Comparison of the effects of ethylene and tetradeuterioethylene revealed that the emission quenching was due to enhanced vibrational relaxation. The Ag(I) ions are essential to the observed optical response. The oligomer/polymer support enhances the response characteristics of the impregnated salt by promoting separation of Ag(I) from its anion, a separation that improves accessibility of the Ag(I) ion to the gaseous analytes. Salts with large lattice energies, where the anion is not dissociated from Ag(I) in the matrix, fail to sensitize film responses. Photoluminescence experiments with Ag(I)-impregnated BMSB films established that the Ag(I) ions serve to communicate the analyte-binding signal to the support by altering the support-based emission. These experiments demonstrate a sensing paradigm where simultaneous coordination of Ag(I) ions to the support matrix and to a gaseous analyte enables the optical response.