Several high-explosive (HE) crystals are known to be piezoelectric. However, no systematic study has been carried out on how this effect can be utilized. In this paper, we report the results of an analysis on the response of composites consisting of HE crystals and a polymeric binder under electrostatic excitation. The HE crystals considered are 1,3,5-trinitroperhydro-1,3,5-triazine, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, pentaerythritol tetranitrate, and ammonium perchlorate. To explore avenues for enhancing the piezoelectric effect, the binder of the composites is taken to be piezoelectric polyvinylidene fluoride. The focus is on the distributions of induced electric field vector and mechanical stress in the microstructures. The effects of crystal–binder volume fraction, HE crystal size, and dielectric constants of the HE crystals are investigated. To further explore the effect, microparticles of lead zirconate titanate piezoelectric ceramic are introduced to some microstructures. For the HE crystals considered here, a coupled electromechanical analysis shows that the microstructural heterogeneities can enhance the local electric fields to as high as 1.34 times the applied E-field, causing the dielectric breakdown field strength of the overall composite to be much lower than the breakdown strengths of the constituents in the microstructure. In addition, the induced stress levels just prior to dielectric breakdown are well below the yield strengths of the respective constituents. As such, controlled dielectric breakdown, rather than mechanical damage, should primarily be used to facilitate hotspot formation, ignition, and chemical reaction. The likelihood of local dielectric breakdown within the HE crystals is systematically quantified as a function of applied electric field, microstructural attributes, and constituent behavior. To gauge the effect of the direct piezoelectric effect, one material case is also subjected to mechanical excitation in the form of compression. Under an applied external stress, the results show that the direct piezoelectric effect can lead to local yielding and thereby serve as a hotspot generation mechanism. On the other hand, the induced E-field is weak and unlikely to serve as a practical or efficient means of effecting hotspots within an energetic material. The analysis points out that simultaneous application of electrostatic excitation and mechanical excitation can also be considered.