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The combination of metal oxides Bi2O3:Li2O in a ratio 89:11 gives a eutectic with a melting point of ∼680°C. Such a low melting point oxide combination creates a working liquid phase at a highly favorable temperature for use as a densification aid. A liquid—phase sintering aid incorporating Bi2O3 and Li2O is presented which demonstrates not only a reduction in the required sintering temperature but also shows relatively higher ‘c/a’ ratio (tetragonality) of PbTiO3 ceramics with no fragility of the samples. Detailed dilatometric investigations have been performed in order to study the dominant shrinkage mechanism in the present system. Besides acting as a liquid phase fluxing agent, Bi2O3/Li2O also behave as Curie shifter, which decreases Curie temperature in lead titanate system. The Curie temperature has also been verified from the thermal expansion behavior of sintered specimens. The value of dielectric constant increases after poling which may be due to the dominance of 180° domain wall over 90°.