The global energy crisis and climate change pose unprecedented challenges. Wearable devices with personal thermoregulation and energy harvesting hold great promise for achieving energy savings and human thermal comfort. Here, inspired by neurons, a novel phase change material (PCM) is reported for efficient energy harvesting and respiratory monitoring via a self-assembly strategy. The use of gum arabic (GA) enabled the encapsulation of polyethylene glycol (PEG) and the targeted distribution of carboxylated multi-walled carbon nanotubes (cMWCNTs) simultaneously in poly (ethylene vinyl acetate) (EVA) matrix. The material exhibits an outstanding toughness value of 14.88MJ m-3 and high elongation at a break of 565.67%, exhibiting remarkable flexibility. The material with sufficient melting enthalpy (71.11 J g-1) demonstrates high photothermal conversion efficiency (95.27%) under 808nm laser irradiation (105mW cm-2). In addition, due to the synergistic effect of GA and PEG, especially the formation of microdome structures on the surface, the material demonstrates ultrasensitive humidity responsiveness for respiratory monitoring with high precision, excellent repeatability, and fast response/recovery time (50.4/50.5ms). Notably, it shows great potential for moisture-electric generators (MEGs) with the function of non-contact sensing. This material opens the path toward next-generation wearable devices in energy conversion and health monitoring.