In this study, the synthesis of composite biomaterials consisting of hydroxyapatite (HA)/carbonated hydroxyapatite (CHA) with polymeric porous scaffolds is reported. Multicomponent biodegradable polymers were applied as the scaffold. These consist of alginate and chitosan. The effect of polyvinyl alcohol (PVA) involvement in the multicomponent polymeric scaffold was also investigated. The scaffold was loaded with HA/CHA, as bone graft materials, at various compositions. Asian moon scallop shell (Amusium pleuronectes) was used as a calcium biogenic resource for HA and CHA synthesis The effect of the PVA and HA/CHA concentration was investigated. In the absence of the PVA, the morphological study showed that the samples had porous structures with good pore interconnectivity. The XRD analysis showed that PVA reduced the crystallinity of the bone graft. The HA/CHA crystals were homogeneously dispersed. The introduction of PVA reduced the pore size and the porosity but provide stiffer materials, indicating that PVA may improve the mechanical properties of the composite. Some samples also showed the presence of small and large pores. The weight percentage content of HA or CHA influenced the crystallinity, indicating the possibility for the fabrication of tailored bone substitute materials.