In this work, polyvinyl pyrrolidone (PVP) capped zinc selenide (ZnSe) nanorods were synthesized with varying molar concentrations of Zn precursor through chemical reaction. X-ray Diffraction (XRD) revealed the cubic polycrystalline nature of synthesized ZnSe nanostructures. Structural morphology indicated the formation of nanorods along with spherical nanoparticles with sizes ranging from 8 nm to 40 nm. The absorption spectra demonstrated a notable blue shift signifying the reduction in bandgap with the increased Zn2+ ion concentration while the refractive index showed a proportional rise. The photoluminescence (PL) spectra revealed the near bandgap emission at 416 nm along with other defect-related emissions. The conduction mechanism, assessed through I–V characteristics, suggested Richardson-Schottky or electrode limitation in the high bias region within the ZnSe nanocrystals. These findings could potentially facilitate the customization of ZnSe nanorods for optoelectronics device application.