Advancements in isotope separation are both essential and challenging. The separation of water isotopes is vital in industrial production, biopharmaceuticals, and healthcare applications. This process is energy-intensive and complex due to the similarity of the isotopes. Pure polyacrylonitrile (PAN) is resistant to proton permeability, but neutral hydrogen radicals are capable of penetration. In this study, we report a novel approach using PAN macroscopic hybrid micro-/nanofibers in combination with a photocatalyst to separate hydrogen ion isotopes. Application of photocatalytic water splitting to generate protons results in significantly slower deuteron permeation in these fibers relative to protons, resulting in a separation factor of approximately 15 at room temperature. The composite PAN fibers exhibit a conductivity of 17.5 mS cm−1 at 25 °C and 95 % relative humidity. Our approach not only converts sunlight directly into storable hydrogen, but also enriches heavy water from H₂O/D₂O by H/D isotope separation. This study provides new insights into proton transport mechanisms in acidic media and demonstrates the significant potential of high molecular weight polymers for hydrogen isotope separation.