Glass‐ceramic 3D porous structures were obtained by from a polymeric template, which was successively loaded with calcium phosphates, by chemical reaction and a dried gel based on barium and titanium by physical attachment. The resulting composite was subjected to a freeze‐drying procedure in order to maintain the spongy morphology. Under the effect of the subsequent thermal treatment at temperatures above 1000°C, the biocellulose membrane was completely removed, the mineral phases combined with each other through intense diffusion processes, and the mineral scaffolds acquired enough mechanical strength to become self‐sustained. The as‐prepared and thermally treated samples were characterized from physicochemical and biological point of view. The only crystalline phase emerged in the final masses was TiO2, while the microstructure was individualized as peculiar 3D architectures with porous and branched appearance. All prepared materials were proven to be biocompatible with the mesenchymal stem cells, showing no cytotoxic effect and suitability for the field of tissue engineering.