In this study, two structurally different scaffolds, a polycaprolactone (PCL)/45S5 Bioglass (BG) composite and PCL/hyaluronic acid (HyA) were fabricated by 3D printing technology and were evaluated for the regeneration of dentin and pulp tissues, respectively. Their physicochemical characterization was performed by field emission scanning electron microscopy (FESEM) equipped with energy dispersive spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), contact angle, and compressive strength tests. The results indicated that the presence of BG in the PCL/BG scaffolds promoted the mechanical properties, surface roughness, and bioactivity. Besides, a surface treatment of the PCL scaffold with HyA considerably increased the hydrophilicity of the scaffolds which led to an enhancement in cell adhesion. Furthermore, the gene expression results showed a significant increase in expression of odontogenic markers, e.g., dentin sialophosphoprotein (DSPP), osteocalcin (OCN), and dentin matrix protein 1 (DMP-1) in the presence of both PCL/BG and PCL/HyA scaffolds. Moreover, to examine the feasibility of the idea for pulp-dentin complex regeneration, a bilayer PCL/BG-PCL/HyA scaffold was successfully fabricated and characterized by FESEM. Based on these results, it can be concluded that PCL/BG and PCL/HyA scaffolds have great potential for promoting hDPSC adhesion and odontogenic differentiation.