The electrochemical behavior of 1,4-dinitrobenzene (1,4-PNB) on the Au electrode was investigated by cyclic voltammetry (CV), in situ FT-IR spectroelectrochemistry, cyclic voltabsorptometry (CVA) and derivative cyclic voltabsorptometry (DCVA) techniques. In aprotic media, 1,4-dinitrobenzene is reversibly reduced in two-step one-electron transfer. A series of IR absorption bands at 1056, 1210, 1341, 1356, 1464 and 1549 cm(-1), tracing to PNB; PNB center dot- and PNB2- are observed. In the presence of proton donors mixed media, with increasing concentrations of proton donors, hydrogen-bonding and protonation process are found successively. The values of combining proton donors with per PNB2- to form hydrogen-bonding are estimated by using electrochemical parameters. The result of forming aromatic nitroso compound is supported by tracing the change of IR absorption bands at 1149 and 1587 cm(-1) at high concentration of proton donors. Based on CVA and DCVA techniques, it is clearly distinguished that the mechanisms of electrochemical reduction of PNB are elaborated in different systems. (C) 2011 Elsevier Ltd. All rights reserved.