Poly(diphenylamine) (PDPA) film was deposited on indium doped tin oxide coated glass electrode in 1 M perchloric acid by cyclic voltammetry. Cyclic voltammograms (CVs) of the PDPA film were recorded with different potential limits and the redox transitions in PDPA were identified. The spectroscopic changes accompanying the redox transitions were followed at different applied potentials using UV–visible spectroscopy. Dynamic cyclic spectrovoltammetry was used to deduce the derivative cyclic voltabsorptogram (DCVA). The absorbance changes are represented by constructing a novel absorbance–potential–wavelength profile. In the profile, the CV showing the redox transitions is presented side by side to identify the electrochromic sites in PDPA in an easy way. The results deduced are compared with the conventional DCVA. Identifying the electrochromic sites brought out the differences in electrochromic behavior between PDPA and PANI.