A novel composition of co-polyurethane modified phosphorus pentasulfide is formed. The formed polyurethan is the source of N and O elements in the formulation, while phosphorus pentasulfide is the source of P and S. A rich P, S, N, and O element polymeric material of co-polyurethane is synthesized. The isocyanate part is toluene diisocyanate, and the polyol part is a mixture of novolac phenol formaldehyde resin and polyethylene glycol 600. The synthesized material is characterized using Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and thermal analysis of differential scanning calorimetry (DSC) elemental analysis. Phosphorus, sulfur, nitrogen, and oxygen elements are electron donor negative charged elements that have free pairs of electrons which are able to share in the molecule resonance and conjugation, increasing the optical, electrical, and other desired properties. The energy gaps computed for direct and indirect transitions were 2.25 and 2.205 eV, respectively. The optical energy gap value and the band energy tails decrease with modified phosphorus pentasulfide (PPS). The observed electrical conductivity of the composites at different temperatures is generally close to that of semiconducting materials, and the activation energy was computed. They may therefore be interesting materials for electrical applications.