Hybrid nanocomposite films containing polythiophene/gold nanoparticles and polythiophene/gold nanoparticles/carbon nanotubes, synthesized through a liquid-liquid interfacial polymerization route at different reaction times and amounts of carbon nanotubes, were investigated through spectroscopic and morphological techniques. X-ray photoelectron spectroscopy showed the formation of polythiophene aggregates and the presence of large gold particles, corroborating the results of transmission and scanning electron microscopy. Near-edge X-ray absorption fine structure showed films without any preferential molecular orientation of the polymer chains. The bandgap obtained by reflection electron energy loss spectroscopy is reduced with the increase in the synthesis reaction time and the decrease in the amount of carbon nanotubes, which is followed by ultrafast electron dynamics studied with the core-hole clock method. These films were heat-treated at 200 °C for 30 min and faster charge transfer times were observed. Current x Voltage curves showed a photoactive response of the materials.