Background Vascularization is a crucial factor when approaching any engineered tissue. Hybrid biomaterials composed of biodegradable synthetic polymers and inorganic materials showed suitable properties for biomedical application. Being Vascular Wall – Mesenchymal Stem Cells derived from pig thoracic aorta (pVW-MSCs) an excellent in vitro model to study vascular remodelling due to their strong angiogenic attitude, the aim of the present study was to demonstrate the angiogenic potential of experimental highly porous scaffolds based on polylactic acid (PLA) or poly-e-caprolactone (PCL) doped with calcium silicates (CaSi) and dicalcium phosphate dehydrated (DCPD), namely PLA-10CaSi-10DCPD and PCL-10CaSi-10DCPD. Results The results obtained clearly demonstrated that the cells colonized the scaffolds and were metabolically active. Moreover cells, grown in these 3D systems, showed the typical gene expression profile they have in control 2D culture, although with some main quantitative differences. DAPI staining and immunofluorescence assay confirmed cellular presence on both scaffolds, however pVW-MSCs cultured in PLA-10CaSi-10DCPD showed an individual cellular growth, in contrast, in PCL-10CaSi-10DCPD scaffolds pVW-MSCs grew in spherical clusters. Conclusion In conclusion, the property of the experimental scaffolds demonstrated the suitability of the scaffolds to be colonized by vascular stem cells for new vessels formation and a potential application in tissue regeneration for biomedical purpose.