Limonene-based polymers have a growing interest as being renewable source-derived materials. Here, highly cross-linked porous polymers were synthesized by free radical copolymerization of water-in-oil (w/o) high internal phase emulsions (HIPEs) of limonene and ethylene glycol dimethacrylate (EGDMA). The bio-derived monomer content in the total monomer composition was set to 50 vol%. To vary the openness and permeability of the resulting porous copolymers, synthesized poly(limonene-co-EGDMA) (PLE-x) copolymers were processed via two different approaches as extraction (E) and lyophilization (L). Ultimately, the ring-porous PLE-E or PLE-L copolymers with different degrees of permeability were used as supporting matrices for the development of form-stable palmitic acid@poly(limonene-co-EGDMA) (PA@PLE-E and PA@PLE-L) composite phase change materials (PCMs). The chemical structure, pore morphology, specific surface area, and thermal properties of the PLE based supports and PA@PLE-E / PA@PLE-L composite PCMs were explored. BET specific surface areas of the ring-porous PLE-E and PLE-L frameworks were measured to be 20.5 m2.g−1 and 4.8 m2.g−1. In addition to that, the latent heats of the resulting composite PCMs were found to be 77.4 J.g−1 and 64.1 J.g−1, while the peak melting temperatures were 63.4 °C and 60.7 °C, for PA@PLE-E and PA@PLE-L, respectively. The bio-derived matrices based thermally stable leak-proof PA@PLE-x composite PCMs with proper latent heat storage (LHS) characteristics are ideal candidates as energy materials for passive solar heating applications due to their favorable phase change temperatures.