This work proposes the use of multilayer scaffolds as a strategy for developing biomimetic structures for bone tissue regeneration. The scaffolds consist of a glass–ceramic core composed of CaSiO3/Ca2P6O17, which provides mechanical properties of 2.3 MPa and a total porosity of ∼74%. To modify the surface morphology a double bioactive coating consisting of Ca3(PO4)2/CaSiO3 doped with Na+ and K+, along with varying amounts of Mg2+ (0–0.75 g MgCO3) was carried out giving a total porosity of 89.8%. The resulting scaffolds were assessed for in vitro bioactivity according to ISO 23317. After immersion in SBF, the W‐05 scaffolds displayed diverse surface morphologies: square HA structure (W‐05‐3D), hollow HA spheres (W‐05‐7D) and smooth HA layer (W‐05‐21D). Cell viability of 3T3 fibroblasts exposed to W‐05 scaffolds in direct and indirect assays at concentrations of 15 and 30 mg/mL was assessed according to ISO 10993–5. Initially, cell proliferation decreased compared to controls, but differences became non‐statistically significant after 72 h. Hollow spheres (W‐05‐7D) enhanced cell viability compared to other morphologies and plastic controls. Additionally, degradation products of W‐05 stimulated cell division, underscoring scaffold biocompatibility.