Abstract This experimental investigation evaluates the strain and damage sensing abilities of multi-walled carbon nanotube (MWCNT) networks embedded in the binder phase of polymer-bonded energetics (PBEs). PBEs are a special class of particulate composite materials that consist of energetic crystals bound by a polymer matrix, wherein the polymer matrix serves to maintain the composite’s shape and form. The structural health monitoring (SHM) approach presented in this work exploits the piezoresistive properties of the distributed MWCNT networks. Major challenges faced during such implementation include the low binder concentrations of PBEs, the presence of conductive/non-conductive particulate phases, the high degree of heterogeneity in the PBE microstructure, and achieving the optimal MWCNT dispersion. In this study, ammonium perchlorate (AP) crystals as the oxidizer, Aluminum grains as the metallic fuel, and Polydimethylsiloxane (PDMS) as the binder are used as the constituents for fabricating PBEs. To study the effect of each constituent on the MWCNT network’s SHM abilities, various materials systems are comprehensively studied: MWCNT/PDMS materials are first evaluated to study the binder’s electromechanical response, followed by AP/MWCNT/PDMS to assess the impact of AP addition, and finally, AP/AL/MWCNT/PDMS to evaluate the impact of adding conductive aluminum grains. Compression samples (ASTM D695) were fabricated and subjected to monotonic compression. Electrical resistance is recorded in conjunction with the mechanical test via an LCR meter. Gauge factors relating to the change in normalized resistance to applied strain are calculated to quantify the electromechanical response. MWCNT dispersions and mechanical failure modes are analyzed via scanning electron microscopy imaging of the fracture surfaces. Correlations between the electrical behavior in response to the mechanical behavior are presented, and possible mechanisms that influence the electromechanical behavior are discussed. The results presented herein demonstrate the successful ability of MWCNT networks as SHM sensors capable of real-time strain and damage assessment of PBEs.