Phase change energy storage technology using phase change materials (PCMs) is a viable solution to effectively address the heat dissipation problems of electronic devices. Herein, we proposed to prepare a modified PCM using CH3COONa·3H2O (SAT) as main PCM, 9 wt% DL-Alanine (DL) as temperature modifier, and 2 wt% Na2HPO4·12H2O as nucleating agent. Calculations using density functional theory method confirmed that the adjustment of DL on phase change temperature of SAT was originated from the hydrogen bond between them. Then, the modified PCM was loaded into 14 wt% expanded graphite (EG) to obtain a composite PCM with a suitable phase change temperature of 52.9 °C, phase change enthalpy of 227.4 J/g as well as supercooling degree of 6.6 °C, and the thermal conductivity of the composite PCM was as high as 11.52 W·m−1·K−1. SEM and pore structure analyses showed that the modified PCM was successfully loaded into the pore structure of EG, and their combination was verified by XRD and FT-IR as a physical interaction. After 200 heating–cooling cycles, the phase change temperature and enthalpy of the composite PCM was basically unchanged along with consistent crystal structure and chemical composition, showing an excellent thermal reliability. A comparative analysis applied in a testing system showed that with loading of the composite PCM temperature control module, the critical time of the electronic chip was extended by 4670 s and the thermal equilibrium temperature was decreased by 20.4 °C, presenting a good thermal management performance. Therefore, the prepared composite PCM had great potential for application in thermal management of electronic devices.