The thermal storage performance, cost, and stability of phase-change materials (PCMs) are critical factors influencing their application in the field of thermal energy storage. Porous carbon, with its excellent support, thermal conductivity, and energy storage properties, is considered one of the most promising support matrix materials. However, the simple and efficient synthesis of high-performance and highly active bio-based materials under mild conditions still faces challenges. In our work, a novel method for preparing new functional composite phase-change materials based on enzyme treatment technology and using waste walnut green husk biomass and polyethylene glycol as raw materials was developed. The enzymatic treatment method exposes the internal structure of the walnut green husk, followed by the adjustment of the calcination temperature to increase the adsorption sites of the biochar, thereby stabilizing polyethylene glycol (PEG). The porous properties of walnut green husk biochar effectively regulate the phase-change behavior of polyethylene glycol. In the biochar carbonized at 600 °C, the PEG loading reached 72.09%, and the absorption heat of the solid–solid phase-change material (SSPCM) reached 194.76 J g−1. This work not only enriches the application of biomass in heat storage but also demonstrates the broad prospects of SSPCMs in solar thermal utilization.