Physiological bioengineering of multilayered tissues requires an optimized geometric organization with comparable biomechanics. Currently, polymer-reinforced three-dimensional (3D) graphene foams (GFs) are gaining interest in tissue engineering due to their unique morphology, biocompatibility, and similarity to extracellular matrixes. However, the homogeneous reinforcement of single polymers throughout a GF matrix does not provide tissue-level organization. Therefore, a triple-layered structure is developed in a GF matrix to closely mimic native tissue structures of the periodontium of the teeth. The scaffold aims to overcome the issue of layer separation, which generally occurs in multilayered structures due to the poor integration of various layers. The 3D GF matrix was reinforced with a polycaprolactone (PCL), polyvinyl alcohol (PVA), and PCL-hydroxyapatite (HA) mixture, added sequentially, via spin coating, vacuum, and hot air drying. Later, PVA was dissolved to create a middle layer, mimicking the periodontal fibers, while the layers present on either side resembled cementum and alveolar bone, respectively. Scanning electron microscopy and micro-computed tomography revealed the structure of the scaffold with internal differential porosities. The nanoindentation and tensile testing demonstrated the closeness of mechanical properties to that of native tissues. The biocompatibility was assessed by the MTT assay with MG63 cells (human osteosarcoma cells) exhibiting high adhesion and proliferation rate inside the 3D architecture. Summing up, this scaffold has the potential for enhancing the regeneration of various multilayered tissues.