Phase change materials (PCMs) have gained significant attention as thermal energy storage materials for reducing dependence on fossil fuels. However, the leakage caused by long-term molecular motion has become a bottleneck for the further advances of energy storage density and application value. Herein, a novel PCM composite with good shape stability, thermal conductivity and photothermal conversion capability was designed. Given the synergistic or hybridization effect between metal-organic frameworks (MOFs) and expanded graphite (EG) components offered the composite unique capabilities, even with the merits of both. The combination of ZIF-67 and EG in a hybrid structure can effectively prevent particle agglomeration, while simultaneously providing a high specific surface area and pore volume for the adsorption of paraffin wax. Compared to pristine unsupported PCMs, the as-obtained PCM composite possesses a 3-fold enhancement in thermal conductivity, 95.56% photothermal conversion efficiency and excellent shape stability. It demonstrates the potential of MOFs-enhanced PCM composites for thermal energy storage and highlight the importance of synergistic or hybridization strategies in the development of advanced materials for sustainable energy applications.