Using (+)-catechin electrodeposited on a carbon-paste electrode as a model system, we have demonstrated the usefulness of the time-derivative cyclic voltabsorptometry for voltammetric characterization of the deposited films, in the case when not only the deposited species but also the same ones in free solution participated in redox processes. A long-optical-path thin-layer cell was used for the voltabsorptometric measurements. The potential-dependent absorption signals were monitored for catechin at 252 and 279 nm in B-R buffer electrolytes with pH = 1.8. The combination of voltabsorptometry with voltammetry enabled one measured cyclic voltammogram to become four, which were attributed to catechin and its oxidized state, in free solution or in deposited state, respectively. The surface coverage of the electrode was evaluated from the cyclic voltammograms obtained for the deposited catechin, which decreased with the increasing scan rate. Also, the deposited species was found to make a major contribution to the total voltammetric current, especially at higher scan rates.