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Subsolidus equilibria in the PbO-poor part of the TiO2–PbO–SiO2 diagram were studied with the aim of investigating possible applications for low-temperature thick-film dielectrics. The tie lines are between PbTiO2 and PbSiO3, and between PbTiO3 and SiO2. The results show that the TiO2, when added to low- temperature softening point glasses, reacts with the PbO from the glass, so forming PbTiO3. These results were applied to a low-temperature firing dielectric, consisting of a lead-rich PbO–SiO2–B2O3 glass filled with a TiO2 powder. The conversion of TiO2 to the PbTiO3 crystalline phase was observed above firing temperatures of approximately 600°C. The kinetics of the reaction depend on the particle size of the TiO2.