Poly(𝑜-toluidine) (POT) polymer was synthesized by chemical method and RF plasma polymerization at a radio frequency (RF) power input of 15 W on ultrasonically cleaned glass and silicon wafer substrates. These samples were characterized by DC conductivity measurements, UV–visible, XRD and FTIR techniques. The DC-conductivity was measured at 410 K, which was found to increase by two orders of magnitude for thin film as compared to pellet samples. It has been observed that the activation energy increases for RF plasma-polymerized POT. Transmission and reflectance spectra were studied for measuring optical constants like absorption coefficient (𝛼), extinction coefficient (𝐾), optical band gap (𝐸_g), Urbach energy (𝐸_e), and refractive index (𝑛). From XRD studies, one can infer that the samples grown by both the methods are amorphous in nature. The results indicate that the structures of plasma-polymerized POT are rather different from polymers synthesized by conventional chemical methods, due to a higher degree of cross-linking and branching reactions in plasma polymerization. This makes them suitable for various electroactive devices. A higher and more stable conductivity can be obtained with RF plasma-polymerized POT which is much smoother and more uniform.