Solar energy is the only renewable and carbon-neutral energy source of sufficient amount to replace fossil fuels. The development of solar energy conversion and storage materials is critical to narrow the mismatch between supply and demand of energy and alleviate the environmental impact related to energy consumption in the coming years. Here, a novel photodriven composite phase change materials (PCMs) based on bioinspired modification of boron nitride (BN) with superior solar-thermal energy conversion and storage performance is reported. The obtained composite PCMs show excellent performance in UV-vis sunlight harvesting, photothermal conversion, thermal energy storage, high thermal conductivity, electrical insulation, and shape-stabilization. The procedure is eco-friendly, easy handling, and suitable for the practical application of energy materials based on novel polyethylene glycol (PEG)/(polydopamine)PDA@BN composites with enhanced performance for energy conversion and storage in large scale.