The fabrication of nanostructured block copolymer (BCP) films endowed with lithium ion‐conducting gyroid (GYR) nanochannels is an appealing solution to build solid polymer electrolytes (SPEs) that combines high ionic conductivity (IC) with suitable mechanical properties. However, the formation of a well‐developed GYR structure remains challenging to achieve from the self‐assembly of polyelectrolyte BCP chains. To overcome this issue, large ion conducting gyroid grains were produced within freestanding polystyrene‐ block ‐poly(2‐vinylpyridine)‐ block ‐poly(ethylene oxide) (PS‐ b ‐P2VP‐ b ‐PEO) films by combining a solvent vapor annealing (SVA) treatment with an infiltration process. Here, the SVA treatment enabled the manufacture of SPEs entirely composed of a GYR structure while the infiltration process allowed for the incorporation of an appropriate Li salt (i.e., lithium iodoacetate, LiIAc) within the 3D‐interconected nanochannels via a Menshutkin reaction. By using this SVA‐Infiltration strategy, it has been demonstrated that the creation of ion conducting GYR nanochannels enhances the ion transportation capacity of pyridine‐containing SPEs since substantially lower ICs were measured from analog PS‐ b ‐P2VP‐ b ‐PEO/LiIAc films having a nominally disordered as‐cast state. Remarkably, zwitterionic pyridinium‐based moieties formed inside the interpenetrated nanochannels enable an efficient migration of Li + and I 3 − species, leading to an IC as high as 10 −4 S cm −1 at 70°C.