ZnO and TiO₂ are both well-known electron transport materials. Their comparison of performance is considered advantageous and novel. Therefore, a viable electrospinning route was considered for the development of highly polycrystalline TiO₂ and ZnO nanofibers as an electron transport material (ETM) for perovskite solar cells. The materials were well-characterized in terms of different analytical techniques. The X-ray diffraction detected polycrystalline structural properties corresponding to TiO₂ and ZnO. Morphological analysis by scanning electron microscopy revealed that the nanofibers are long, uniform, and polycrystalline, having a diameter in the nanometer range. Optoelectronic properties showed that TiO₂ and ZnO exhibit absorption values in the ultraviolet and visible ranges, and band gap values for TiO₂ and ZnO were 3.3 and 3.2 eV, respectively. TiO₂ bandgap and semiconductor nature were more compatible with Electron Transport Layer (ETL) compared to ZnO. Electrical studies revealed that TiO₂ nanofibers have enhanced values of conductivity and sheet carrier mobility compared to ZnO nanofibers. Therefore, higher photovoltaic conversion efficiency was achieved for TiO₂ nanofibers (10.4%) compared to ZnO (8.5%).