This study explores the impact of Zinc Oxide (ZnO) coating on photovoltaic energy applications in various silicon nanostructures. Silicon nanostructures (SiNS) were synthesized by an electrochemical etching process, followed by deposition of ZnO coating through the thermal spray pyrolysis at 400 ℃ and the films were characterized via Atomic Force Microscopy, Fourier transform infrared (FTIR) spectroscopy, photoluminescence (PL) spectroscopy, and optical reflectance measurements. The ZnO coating increased the pore diameter from 18.3 nm to 85.3 nm, and the root mean square roughness (RMS) from 0.7 nm to 1.5 nm, as revealed by AFM results. Overall, these modifications allowed for the improvement of the anti-reflective characteristics of the silicon surface, thus reducing its reflection and encouraging its ability to absorb incoming light. FTIR characterized that ZnO was deposited successfully, and the zinc silicate (Zn2SiO4) formed from the silica at the interface, enhancing the material’s stability and interface adhesion between the ZnO layer. When photoluminescence measurements were taken, a redshift of the emission peak with the metallic oxide deposition was observed, indicating enhanced photo-conversion efficiency. Optical reflectance measurements revealed a noticeably lower reflectance, especially in the 400–600 nm band, as a result of improved scattering and transmittance of light. The tests on solar cells showed a short-circuit current (Isc) and an open-circuit voltage (Voc) spanning a fill factor (FF) of 78.7% and conversion efficiency (η%) of 16.1%, suggesting the utility of ZnO-coated silicon nanostructures to develop high-performance solar cells.