Polycaprolactone (PCL), dicalcium phosphate dihydrate (DCPD) and/or calcium silicates (CaSi) have been used to prepare highly porous scaffolds by thermally induced phase separation technique (TIPS). Three experimental mineral-doped formulations were prepared (PCL-10CaSi, PCL-5CaSi-5DCPD, PCL-10CaSi-10DCPD); pure PCL scaffolds constituted the control group. Scaffolds were tested for their chemical-physical and biological properties, namely thermal properties by differential scanning calorimetry (DSC), mechanical properties by quasi-static parallel-plates compression testing, porosity by a standard water-absorption method calcium release, alkalinizing activity, surface microchemistry and micromorphology by Environmental Scanning electronic Microscopy (ESEM), apatite-forming ability in Hank Balanced Saline Solution (HBSS) by Energy Dispersive X-ray Spectroscopy (EDX) and micro-Raman, and direct contact cytotoxicity. All mineral-doped scaffolds released calcium and alkalinized the soaking medium, which may favor a good biological (osteogenic) response. ESEM surface micromorphology analyses after soaking in HBSS revealed: pure PCL, PCL-10CaSi and PCL-10CaSi-10DCPD kept similar surface porosity percentages but different pore shape modifications. PCL-5CaSi-5DCPD revealed a significant surface porosity increase despite calcium phosphates nucleation (p < 0.05). Micro-Raman spectroscopy detected the formation of a B-type carbonated apatite (Ap) layer on the surface of PCL-10CaSi-10DCPD aged for 28 days in HBSS; a similar phase (but of lower thickness) formed also on PCL-5CaSi-5DCPD and PCL; the deposit formed on PCL-10CaSi was mainly composed of calcite. All PCL showed bulk open porosity higher than 94%; however, no relevant brittleness was observed in the materials, which retained the possibility to be handled without collapsing. The thermo-mechanical properties showed that the reinforcing and nucleating action of the inorganic fillers CaSi and DCPD improved viscoelastic properties of the scaffolds, as confirmed by the increased value of storage modulus and the slight increase in the crystallization temperature for all the biomaterials. A detrimental effect on the mechanical properties was observed in samples with the highest amount of inorganic particles (PCL-10CaSi-10DCPD). All the scaffolds showed absence of toxicity, in particular PCL-10CaSi-10DCPD. The designed scaffolds are biointeractive (release biologically relevant ions), nucleate apatite, possess high surface and internal open porosity and can be colonized by cells, creating a bone forming osteoblastic microenvironment and appearing interesting materials for bone regeneration purposes.