Crystallization and reaction kinetics of a crystallizable K2O–CaO–SrO–BaO–B2O3–SiO2 glass powder with 17–40 vol% titania powder were investigated. The initially amorphous K2O–CaO–SrO–BaO–B2O3–SiO2 glass powder formed cristobalite (SiO2) and pseudowollastonite [(Ca, Ba, Sr)SiO3] during firing. The above crystalline phases were completely replaced by a crystalline phase of titanite [(Ca, Sr, Ba)TiSiO5] when the amount of added titania was greater than a critical value, e.g., 10 vol%, at 99–1100 °C. A chemical reaction taking place at the interface between titania and the glass was attributed to the above observation. The dissolved titania changed the composition of the glass, and the dissolution kinetics was much faster than the formation of cristobalite and pseudowollastonite. Activation energy analysis showed that the crystallization of titanite [(Ca,Sr,Ba)TiSiO5] was controlled by a reaction-limiting kinetics of formation for the Ti–O bond.