Electrically conducting hybrid composites of poly(3-methoxythiophene) (PMOT) and nickel oxide (NiO) (PMOT-NiO) were synthesized by chemical oxidative method with their different proportions. The synthesized PMOT-NiO nanocomposites were characterized for optical, structural, and electrical analysis. Transmission electron microscope (TEM) depicts the morphology of the samples which revealed the transformation of thread morphology of PMOT to the clusters in PMOT-NiO hybrid composites. The structural and optoelectronic properties of hybrid composites were quite different from those of pure PMOT and NiO nanoparticles which were attributed to the chemical interaction between PMOT and NiO nanoparticle. X-ray diffraction (XRD) confirmed the cubic structure of NiO with an average crystallite size of 5 nm. The nanocomposites had lower diffraction peak intensities and smaller interplanar spacing as compared to NiO. Ultraviolet (UV) spectra and fluorescence spectra (PL) showed that the optical behavior of nanocomposites was far superior to PMOT and NiO separately. FTIR spectra revealed that the absorption of PMOT was affected by the presence of NiO nanoparticle. The roomtemperature electrical conductivity was increased up to 4.2× 10 −7 Ω/cm −1 with increase in the concentration of NiO content in PMOT-NiO hybrid composites.