Sustainability achievement in terms of energy requires consolidated approach for development of efficient materials that are eco-friendly, facile to prepare, and economically executable. With these considerations, this work presents the first report on the yttrium oxide (Y2O3) and zinc oxide (ZnO) stacked nano fibers (Y2O3-ZnO SNFs) prepared via microwave facilitated route. The as prepared material expressed an alleviated band gap energy of 3.68 eV. The synthesized material has mixed cubic and hexagonal phases with an average crystallite size of 38.33 nm. The role of Y2O3-ZnO SNFs as an interface passivating agents was explored in perovskite solar cells reaching 15.4% of the power conversion efficiency (PCE) exhibiting remarkable photovoltaic functionality. In terms of charge storage, Y2O3-ZnO SNFs embellished electrode was fabricated that exhibited excellent stability with the specific capacitance of 310.73 F g−1 with characteristic pseudocapactive behavior. Results for the electrochemical water splitting assays indicated the bifunctionality of Y2O3-ZnO SNFs towards oxygen and hydrogen production. Comparatively improved hydrogen generation was reflected by lower overpotential and Tafel slope values of 146 mV and 127.2 mV dec−1, respectively. Commercialization potential of this material was reflected by the excellent durability and stability checked via electrochemical assays.