In situ spectroelectrochemistry and electrochemical synthesis of conducting polypyrrole (PPy), poly(N-methylpyrrole) (PNMPy), polyindole (PIn) and poly(pyrrole-indole) P(Py-In) on gold and indium tin oxide (ITO) glass electrode have been investigated and compared. The growth rate of all samples has been compared and studied for the first time. Characterization of the filmswas performed by cyclic voltammetry (CV), in situ-UV-Vis spectroscopy, in situ resistance measurements and scanning electron microscopy (SEM). The polymerization reactions are 0.71, 0.76, 0.83 and 0.91 orders with respect to the pyrrole, pyrrole-indole, N-methylpyrrole, indole concentrations and 0.59, 0.62, 0.65 and 0.69 orders with respect to the amount of PPy, P(Py-In), PNMPy and PIn in acetonitrile (ACN) and tetrabutylammonium tetra fluoroborate (TBATFB). The kinetic results indicate that the polymerization growth rate of PPy and P(Py-In) are faster than PNMPy and PIn. The in situ resistivity results indicate that the resistivity of PPy and P(Py-In) polymers was higher by around 1–2.5 orders of magnitude than PNMPy and PIn. The in situ UV-visible spectroscopy of polymers on modified ITO/glass with respect to different potential and time indicate a characteristic absorption’s bands. The morphology of the samples revealed that the polymers were different and well dispersed.