In this study, we synthesized neat and loaded lead phosphate glass (PbO–P2O5) with the inclusion of Cr, Co, Ni, and Zn using an inexpensive sol–gel technique. These composites were then deposited on silica glass substrates. Our objective was to investigate the influence of these fillers on the properties of the glass. The concentrations of the fillers were varied from 0 to 16 wt%, and the resulting thin films were characterized by measuring the absorption coefficient and estimating the optical band gap at room temperature. Additionally, we measured the electrical resistivity of the semiconducting thin films as a function of filler concentrations and temperature. To assess the overall performance of the films, we calculated the figure of merit using the Iles and Soclof approach, considering the DC resistance versus free carrier concentration and absorption coefficient. Interestingly, our results revealed a significant improvement in the figure of merit at specific filler concentrations. The obtained results are comprehensive and provide detailed insights. They indicate that the thin films produced in this study have the potential to be useful in energy devices, particularly in applications involving P–N junctions and similar structures.