Cyclic voltammetric studies of triaminoguanidine nitrate (TAGN), 3,3'-hydrazino bis(bis[6,6'-(3,5-dimethylpyrazol-lyl])-1,2,4,5-tetrazine (HBPT), 4,6-dinitrobenzofuroxan (DNBF) and 3,3'-diamino-4,4'-azoxyfurazan (DAAF) were carried out at different pH conditions in 50% aqueous acetonitrile using glassy carbon electrode. Optimum pH was selected for individual compounds. Influence of scan rate and concentration on the voltammetric response were studied in optimum pH. The number of electron transferred was determined by controlled potential coulometry. All compounds undergo diffusion controlled electrochemical reaction. Based on cyclic voltammetric results, differential pulse and square wave voltammetric methods have been developed for the analytical determination. Instrumental parameters such as initial scan potential, amplitude, pulse increment, pulse period, pulse width and frequency were studied. Optimum experimental conditions for each compound were obtained. After fixing optimum conditions, the effect of concentration was studied and calibration plot was arrived. These plots can be used to determine the traces of the above said four energetic materials. (C) 2007 Elsevier B.V. All rights reserved.