3D printing has been popularly used in the bone tissue engineering, as many of the biomaterials for this field of study can be prepared for and produced from this additive manufacturing technique. In this study, we strategized a solvent-free processing to fabricate the polydopamine-modified calcium silicate (PDACS)/poly-caprolactone (PCL) scaffold with Wharton's jelly mesenchymal stem cells (WJMSCs) incorporated with human umbilical vein endothelial cells (HUVEC)-laden hydrogel. The PDACS/PCL/hydrogel 3D scaffold yielded a Young's modulus of the 3D scaffolds as high as 75 MPa. In addition, the vascular morphogenesis and cellular behaviors regulated by our hybrid scaffolds were also intricately evaluated. Furthermore, the HUVEC in the bioink exhibited higher levels of angiogenic biomarkers and showed potential for the formation of complex vascular networks. Higher levels of bone formation proteins were also observed in our composites. Such a hybrid of synthetic materials with cell constituents not only enhances osteogenesis but also stimulates vessel network development in angiogenesis, presenting the fact that 3D printing can be further applied in improving bone tissue regeneration in numerous aspects. We believe that this method may serve as a useful and effective approach for the regeneration of defective complex hard tissues in deep bone structures.