The effects of TiO 2 addition on the densification, microstructure and microwave dielectric properties of pseudo-wollastonite ceramics (a-CaSiO 3 ) have been investigated. The X-ray diffraction (XRD) patterns results indicate that samples exhibit a two-phase system, which has a wollastonite-structured a-CaSiO 3 primary phase associated with a CaTiSiO 5 minor phase. However, the TiO 2 addition undermines the microwave dielectric properties because of the poor quality factor of the secondary phase of CaTiSiO 5 , which can inhibit the growth of a-CaSiO 3 grains by surrounding their boundaries. The a-CaSiO 3 ceramics containing 2 wt% of TiO 2 sintered at 1,300°C showed excellent microwave dielectric properties: an e r value of 7.86, a quality factor Q 9 f value of 16,491 GHz, and a s f value of 0.76 ppm/°C.