Abstract: Phase change materials (PCMs) provide high latent-heat storage density, but their use in solar-energy systems is limited by low thermal conductivity, insufficient photothermal response, and liquid-state leakage. This review examines photothermal composite PCMs from the perspectives of photothermal mechanisms, structural regulation, and system coupling. It elucidates the photothermal dissipation pathways of metals, semiconductors, carbon materials, transition-metal carbides/nitrides (MXenes), and metal-organic frameworks (MOFs), and summarizes how zero- to three-dimensional structures affect light absorption, directional heat transfer, interfacial thermal resistance, and shape stability. It then contrasts TEG-integrated PCM systems with thermoelectric conversion routes that use no discrete TEG and analyzes the synergistic roles and evidence boundaries of PCMs, liquid cooling, and radiative cooling in photovoltaic (PV) thermal management. The principal limitations are inconsistent test conditions, insufficient multi-day validation, incomplete accounting of parasitic power, and limited longterm service data. Future studies should coordinate spectral response, heat-flow pathways, and phase-transition temperature windows and assess engineering viability based on net energy output and long-term operational stability.