Polymer electrolyte membranes using an ionic liquid as electrolyte with an ionic conductivity anisotropy of ∼5000 have been fabricated using a holographic polymerization nanomanufacturing technique. The resultant structure is referred to as holographic polymer electrolyte membranes (hPEMs), which are comprised of alternating nanolayers of a room temperature ionic liquid and crosslinked polymer resin, confirmed under TEM imaging. These hPEMs also show no reduction in room temperature conductivity with respect to the loaded ionic liquid when characterized in the plane of ionic liquid nanolayers. At elevated temperatures with the optimal electrolyte volume loading, calculation shows that the free ion concentration is higher than the pure ionic liquid, suggesting that the photopolymer dual-functionalizes as a loadbearing scaffold and an ion-complexing agent, allowing for more ions to participate in charge transfer. These hPEMs provide a promising solution to decoupling mechanical enhancement and ion transport in polymer electrolyte membranes.