In order to obtain materials for bone tissue replacement and regeneration that show an appropriate bioactivity, antibacterial behavior and higher mechanical properties than those of the existing bioactive systems, titania–wollastonite materials were obtained by both solid state reaction and sol–gel methods. In the solid state reaction process, titania and wollastonite powders were mixed and sintered. Two different types of materials were obtained by sol–gel: (i) using titanium butoxide, calcium nitrate tetrahydrate and tetraethyl orthosilicate as precursors or (ii) mixing titanium butoxide with wollastonite powder. The in vitro bioactivity was assessed by immersing samples in simulated body fluids for different periods of time. Alamar blue assays and osteoblast-like cells were used for testing citotoxicity. A higher bioactivity was observed on the samples synthesized by sol–gel. However, a higher cell proliferation was observed on the samples obtained by solid state reaction.