Wollastonite (CaSiO3) ceramics are well known biomaterials which can be produced using many different techniques. The present paper illustrates an innovative processing method employing preceramic polymers (silicone resins) containing CaCO3 micro- and nano-sized particles, which act as reactive fillers. Silica from the decomposition of the silicone resins reacts at low temperature with the CaO deriving from the fillers, yielding wollastonite ceramics. Hydroxyapatite powders can also be added, to modify the biological response of the material. This approach enables the fabrication of 3D scaffolds via fused deposition or via conventional hot extrusion.