The integration of conductive carbon supports with organic phase-change materials (PCMs) enables the development of energy conversion and thermal energy storage systems. Herein, we'propose a facile strategy for preparing electro- and photo-driven form-stable PCM composites by loading paraffin wax (PW) into a biomass-derived three-dimensional carbon scaffold. The biomass, raw cotton, was transformed into a hollow carbon fiber (HCF) scaffold by alkaline treatment with subsequent pyrolysis. The resultant HCF scaffold encapsulated a high content of paraffin wax reaching up to 85%. The prepared composites exhibited uniform heat distribution and form-stable phase-change behavior with high energy storage density (up to 182.22 J g(-1)). Moreover, the graphitic character of interconnected HCFs provided thermally and electrically conductive pathways in the PCM matrix. As a result, the HCF-PW composite achieved outstanding energy conversion and storage efficiencies under low input voltage and light intensity. The results provide insightful progress in the utilization of biomass-derived supporting materials to develop photo- and electro-driven PCMs.