Composite materials were prepared from nominal wollastonite powder and glass cullet. Limestone, silica fume and glass cullet were used as raw materials. Wollastonite and pseudowollastonite with traces of cristobalite were phases that developed in the composite materials. The microstructure showed major wollastonite and pseudowollastonite appearing as rounded rod-shaped crystals, spread in a glassy matrix. The density of sintered composite increased from 1.8685–2.5746 g/cm3 and its hardness increased from 462–532 kg/mm2 as the nominal wollastonite ratio decreased. The coefficient of thermal expansion decreased from 8.00–7.30 × 10−6 K−1 as the nominal wollastonite ratio increased.