The studies involve the X-ray photoelectron spectroscopy (XPS) and conductivity measurements of poly(N-methyl aniline) and poly(N-ethyl aniline) films deposited electrochemically at different pH values of -0.96, 2.22, and 3.78 for N-methyl aniline and 1.10, 2.22, and 3.78 for N-ethyl aniline. The results obtained reveal significant differences in the film properties of the two matrices as a function of pH of solution. These differences are explained on the basis of the competitive reaction products formed during polymerization in the two matrices along with the differences in the electron-donating ability of the methyl and ethyl groups present on the nitrogen (N) atom. These results are further supported by the UV-Visible and IR data.