In order to solve the problem of slow heat release rate and difficult temperature control of azobenzene photosensitive molecules, a variety of azobenzene phase change composites with solid-liquid phase change function in different proportions were prepared. Among them, the azobenzene phase-change material prepared in a 3:7 ratio exhibited the highest phase transition point, reaching 73.8°C. These azobenzene phase-change materials demonstrated good cyclic stability, with no significant attenuation in absorbance after 50 cycles of alternating UV and green light excitation. Additionally, they exhibited high energy utilization efficiency, with a minimal enthalpy change of only 11.1 J/g during melting and solidification, enabling maximum energy release. Moreover, the azobenzene phase-change materials showed excellent photothermal conversion efficiency, with a maximum temperature increase of 19°C above room temperature after 500s of exposure to 200 W/m2 xenon lamp light. These materials possess the characteristics of rapid heat release rate and controllable phase transition points, making them promising for a wide range of applications in human thermal management. They can efficiently store the released energy under light stimulation, facilitating photothermal energy conversion.