CdSe nanostructures (NSs) were tuned using different dopants (Fe:CdSe and Mn:CdSe) on electro-synthesized photoelectrochemical cells with fluorine-doped tin oxide (FTO) coated glass and stainless steel substrates. Thin films were characterized for their structural, morphological, and photoelectrochemical characteristics. Their optical and semiconducting parameters were also analyzed to determine the suitability of these films for photoelectrochemical (PEC)/solar cell applications. X-ray diffraction (XRD) analysis revealed that the films are polycrystalline in nature and suitable for improved solar cell applications. Scanning electron microscopy (SEM) studies illustrated that the thin films were adhered to the substrate uniformly and dopants were involved in the formation of novel nanostructured composition. Optical studies showed that the films are of direct band gap. For all the films, the semiconductor parameter values were in the better range of other transition metal chalcogenides, confirming that undoped CdSe and Fe:CdSe, Mn:CdSe thin films are capable as solar/PEC cell materials.