Membrane technology has gained significant importance with the incorporation of ionic liquids into their structure. This work shows the influence of ionic liquid composition on the stability of PVC‐based polymer ionic liquid inclusion membranes (PILIMs) in aqueous solution. Among the ILs investigated, those membranes which contain between 20 and 30%w/w of the least soluble, [OMIM+][PF6−] and [OMIM+][Ntf2−], exhibit losses of IL lower than 10%. For both ILs, the amount immobilized was maximum for the membranes with 30%w/w of IL (0.0838 and 0.0832 g, respectively). On the contrary, the ionic liquid loss increases as its solubility in water increase, reaching 99.52% when PILIMs are prepared with 70%w/w of [OMIM+][BF4−]. The results demonstrate that the stability of PILIMs depends on the solubility of the IL in the surrounding phase and the specific interaction between the IL and the polymeric support for PVC‐to‐IL ratios higher than 30%w/w. © 2016 American Institute of Chemical Engineers AIChE J, 63: 770–780, 2017