We used atomistic molecular dynamics simulations to study the properties of polymerized 1-alkene-3-butylimidazolium-hexafluorophosphate, a polymerized ionic liquid electrolyte, and characterized the influence of the linear alkene length on the mobility of the hexafluorophosphate ions. Consistent with experimental observations, our simulations indicate that as the alkene length increases, the diffusivity of hexafluorophosphate anion monotonically increases. We demonstrate that such a trend arises from the influence of linker segments on the intermolecular ion hopping rates, which is in turn modulated by intermolecular cationic separation distances. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1718–1723. © 2017 Wiley Periodicals, Inc.