The search for safer next‐generation lithium‐ion batteries (LIBs) has driven significant research on non‐toxic, non‐flammable solid electrolytes. However, their electrochemical performance often falls short. This work presents a simple, one‐step photopolymerization process for synthesizing biphasic liquid–solid ionogel electrolytes using acrylic acid monomer and P 111i4 FSI ionic liquid. We investigated the impact of lithium salt concentration and temperature on ion diffusion, particularly lithium‐ion (Li + ) mobility, within these ionogels. Pulsed‐field gradient nuclear magnetic resonance (PFG‐NMR) revealed enhanced Li + diffusion in the acrylic acid (AA)‐based ionogels compared to their non‐confined ionic liquid counterparts. Remarkably, Li + diffusion remained favorable in the ionogels regardless of salt concentration. These AA‐based ionogels demonstrate very good ionic conductivity (>1 mS cm −1 at room temperature) and a wide electrochemical window (up to 5.3 V vs Li + /Li 0 ). These findings suggest significant promise for AA‐based ionogels as polymer solid electrolytes in future solid‐state battery applications.