In this work, a novel electrochemical sensor was developed for the detection of nitroaromatic explosive materials, based on a gold nanoparticle-modified glassy carbon (GC) electrode coated with poly(o-phenylenediamine-aniline film) (GC/P(o-PDA-co-ANI)-Au-nano electrode). Nitroaromatic compounds were detected through their pi-acceptor/donor interactions with o-phenylenediamine-aniline functionalities on the modified electrode surface. The enhanced sensitivities were achieved through pi-pi and charge-transfer (CT) interactions between the electron-deficient nitroaromatic compounds and sigma-/pi-donor amine/aniline groups linked to gold nanoparticles (Au-NPs), providing increased binding and preconcentration onto the modified GC-electrodes. Selective determination of nitroaromatic type explosives in the presence of nitramines was enabled by o-PDA and reusability of the electrode achieved by Au-NPs. Calibration curves of current intensity versus concentration were linear in the range of 2.5-40 mg L-1 for 2,4,6-trinitrotoluene (TNT) with a detection limit (LOD) of 2.1 mg L-1, 2-40 mg L-1 for 2,4-dinitrotoluene (DNT) (LOD=1.28 mg L-1), 5-100 mg L-1 for tetlyl (LOD=3.8 mg L-1) with the use of the GC/P(o-PDA-co-ANI)-AU(nano) electrode. For sensor measurements, coefficients of variation of intra- and inter-assay measurements were 0.6% and 1.2%, respectively (N=5), confirming the high reproducibility of the proposed assay. Deconvolution of current contributions of synthetic (TNT+DNT) mixtures at peak potentials of constituents was performed by multiple linear regression analysis to provide high sensitivity for the determination of each constituent. Determination options for all possible mixture combinations of nitroaromatic explosives are presented in this work. The proposed methods were successfully applied to the analysis of nitroaromatics in military explosives, namely comp B, octol, and tetrytol. Method validation was performed against GC-MS on real post-blast residual samples containing both explosives. (C) 2015 Elsevier B.V. All rights reserved.