Optoelectronic biomaterials have recently emerged as a potential treatment option for neurodegenerative diseases, such as optic macular degeneration. Though initial works in the field have involved bulk heterojunctions mimicking solar panels with photovoltaics (PVs) and conductive polymers (CPs), recent developments have considered abandoning CPs in such systems. Here, we developed a simple antioxidant, biocompatible, and fibrous membrane heterojunction composed of photoactive polymer, poly(3-hexylthiophene) (P3HT), polycaprolactone (PCL) and polypyrrole (PPY), to facilitate neurogenesis of PC-12 cells when photo-stimulated in vitro. The photoactive prototype, referred to as PCL-P3HT/PPY, was fabricated via polymerization of pyrrole on electro-spun PCL-P3HT nanofibers. Four experimental groups, namely PCL alone, PCL/PPY, PCL-P3HT and PCL-P3HT/PPY, were tested. In the absence of the CP, PCL-P3HT demonstrated lower cell survival due to increased intracellular reactive oxygen/nitrogen species production. PCL-P3HT/PPY rescued these cells by virtue of scavenging radicals, where the CP, PPY, acted as an antioxidant. Apart from having better conductivity, the material also enhanced neurogenesis of PC-12 cells when photo-stimulated, compared to the traditional PCL-P3HT. Lastly, the in vitro system with PC-12 was used to demonstrate the practicality of the material for potential use as a cellular patch in optic and nerve regeneration. This work demonstrated the importance of maintaining PV-CP heterojunctions while simultaneously providing a novel platform with possibilities for neural and optic tissue engineering.