As the threat of global climate change due to combustion emissions becomes increasingly alarming, the search for clean and sustainable alternative energy is of paramount importance. With this objective in mind, harnessing solar energy is particularly attractive due to ongoing improvements in silicon‐, perovskite‐, and organic‐based solar cells. Of these, dye‐sensitized solar cells (DSSCs) constitute a promising technology due to their relatively low cost, moderate conversion efficiency, and robust mechanical properties. An important breakthrough in the development of DSSCs is the use of polymer gel electrolytes. In this work, we employ amphiphilic thermoplastic elastomers (TPEs) in the form of sulfonated block ionomer (SBI) homologs for this purpose. Since the midblock of each charged copolymer is hydrophilic, the resultant microphase‐separated nanostructures consist of continuous ionic channels that facilitate electron diffusion. A unique characteristic of the SBI archetype studied here is that the morphology can be solvent‐templated. We exploit this feature by introducing either hydrophilic or hydrophobic photosensitizers into the DSSCs. When the SBI exhibits a primarily lamellar morphology, a hydrophilic dye yields the highest efficiency (7.0%), whereas the opposite is observed when the nanostructure consists of a solvent‐templated nonpolar matrix. Photosensitizer tunability is augmented by the intrinsic mechanical and adhesive properties of a TPE.