AbstractThis work investigated the electrolysis of ammonium dinitramide (ADN: NH4N(NO2)2) in dimethyl sulfoxide (DMSO). Various fundamental electrolysis properties of ADN were assessed based on an electrochemical study and the associated mechanisms were examined based on a quantum chemical approach. ADN exhibited three redox peaks at −0.69, −1.16 and −1.52 V, and two oxidation peaks at 0.34 and 0.50 V (vs Ag/AgCl) at a scan rate of 50 mV s−1 during cyclic voltammetry trials with a platinum electrode. Ultraviolet‐visible spectra of ADN in DMSO were also acquired to determine temporal changes under galvanostatic reduction conditions. These spectra showed that a continuous current in conjunction with an applied voltage of −1.5 V decomposed the ADN, but were unable to elucidate electrolysis products. Quantum chemistry calculations identified possible pathways for the electrolysis of ADN in DMSO, and indicated that reduced ADN rapidly decomposes to form NH3, N2O, NO2 and OH−. The associated Gibbs energy barrier was determined to be almost 0 kJ mol−1 when calculated at the CBS‐QB3//ωB97X‐D/6‐311++G(d,p)/SCRF=(SMD, solvent=dmso) level of theory. These results suggest that ADN can undergo electrolysis in a solvent for which the potential window is sufficiently wide given the application of the appropriate voltage.