The copolymerization technique is an easy way to achieve better properties in a polymer. Copolymers of benzidine with aniline and its substituted derivatives in different comonomer proportions were synthesised using chemical and electrochemical methods. The characterization of the copolymers included elemental, IR, FTIR, XPS, TGA, thermal aging, and electrical conductivity studies. Specific conductivities of copolymers were obtained at different temperatures. Activation energies were calculated from the change in conductivity with temperature. The effect of steric influence on the electrical conductivities of copolymers was observed. Conductivity is also found to be highly dependent on factors Like moisture and % doping. Thermal analysis shows a good thermal stability of the copolymers. The thermal aging process also supports the results obtained from TGA.