The reduction behavior of silver ions to silver nanoparticles is an important topic in polymer/silver salt complex membranes to facilitate olefin transport, as this has a significant effect on the long-term performance stability of the membrane. In this study, the effects ofthe solvent type on the formation of silver nanoparticles, as well as the long-term membrane performance of a solid polymer/silver salt complex membrane were investigated. These effects were assessed for solid complexes of poly(N-vinyl pyrrolidone) $(PVP)/AgBF_4$, using either an ionic liquid (IL), acetonitrile (ACN) or water as the solvent for the membrane preparation. The membrane performance test showed that long-term stability was strongly dependent on the solvent type, which increased in the following order: IL > ACN >> water. The formation of silver nanoparticles was more favorable with the solvent type in the reverse order, as supported by UV-visible spectroscopy. The poor stability of the $(PVP)/AgBF_4$ membrane when water was used as the solvent might have been due to the small amount of water present in the silver-polymer complex membranes actively participating in the reduction reaction of the silver ions into silver nanoparticles. Conversely, the higher stability of the $(PVP)/AgBF_4$, membrane when an IL was used as the solvent was attributable to the cooperative coordination of silver ions with the IL, as well as with the polymer matrix, as confirmed by FTIR spectroscopy.