State-of-the-art multifunctional form-stable phase change materials (FSPCMs) with photo-thermal and electro-thermal dual responses have shown great application potential in sustainable energy utilization. The preparation of photo- and electric-responsive FSPCMs by mixing nano-functional materials such as carbon nanotubes or graphene with phase change materials (PCMs) systems has been extensively studied. Herein, photo and electric dual-responsive nanocapsules (IPW@CLPS@PPy) were designed and constructed by employing industrial paraffin wax (IPW) as the core PCMs, crosslinked polystyrene (CLPS) as the supporting inlayer via miniemulsion polymerization, and polypyrrole (PPy) as the dual functional outlayer via further fast-oxidative chemical polymerization. The resultant IPW@CLPS@PPy exhibits good shape stability, ideal phase change enthalpy (114.2 J/g), excellent thermal stability, and cyclability. Furthermore, the PPy functional outlayer endows IPW@CLPS@PPy nanocapsules with excellent solar light absorption capacity and electrical conductivity, resulting in ideal photo-thermal conversion efficiency (88.4%) and electro-thermal conversion efficiency (80.1%). Consequently, the synthesized IPW@CLPS@PPy has broad application prospects in photo-thermal and electro-thermal conversion/storage fields. This study will not only provide new ideas for the design and synthesis of nanostructured multifunctional FSPCMs but also open up routes towards the development of FSPCMs for energy harvesting, conversion, and storage fields. Herein, IPW was encapsulated by CLPS inlayer via a simple free-emulsifier miniemulsion polymerization, and the nanocapsules were further covered by PPy outlayer via a fast-oxidative chemical polymerization, thus the photo/electric dual-responsive FSPCM (IPW@CLPS@PPy) was prepared. The resultant IPW@CLPS@PPy features excellent shape stability, ideal thermal performance, and photo/electro-thermal conversion ability as well as stability, which promises wide application in the photo and electro-thermal conversion/storage. This research may provide more information for the construction of nanostructured multifunctional FSPCMs and open a new window of energy conversion/storage in different charging modes. • Industrial paraffin wax, cross-linked polystyrene, and polypyrrole formed an integrated composite. • The composite had excellent shape stability, thermal stability, and cyclability. • The composite exhibited high photo/electro-thermal energy conversion efficiency. • The composite possessed ideal functional stability.