Ultrasensitive explosive sensors are significant in anti-terrorism and related environment issues. Herein, we proposed a novel boron-doped graphene (B-GE) modified glassy carbon electrode (GCE) applied as a simple, sensitive electrochemical high melting explosive (HMX) sensor. The morphology and structure features of B-GE were characterized. The electrochemical behaviors of HMX on the B-GE modified GCE were investigated by cyclic voltammetry (CV). Under the optimized conditions, CV was used for the quantitative detection of HMX, and the reduction peak current exhibited good linear dependence with the concentration of HMX in the ranges of 2 similar to 20 mu M and 20 similar to 100 mu M. The low detection limit (LOD) was calculated as 0.83 mu M (245.81 ppb). Furthermore, the B-GE/GCE showed satisfactory repeatability, high selectivity and stability. The reduction reaction mechanism of HMX on B-GE modified electrode was explored by computational theoretical analysis. Additionally, the differences of the reduction mechanisms from nitroaromatic explosives were discussed. (C) 2016 Elsevier Ltd. All rights reserved.