The polycrystalline ferroelectric compounds of general formula Pb1−XBaXTiO3 with X = 0.00, 0.1, 0.2 and 0.5 were prepared by high temperature solid-state reaction technique using high purity oxides and carbonates. The compounds formation was confirmed by X-ray diffraction and all the X-ray peaks were indexed with tetragonal structure of space group P4mm. Morphology and particle size of the compounds were obtained using scanning electron microscopy. Ferroelectric phase transition, enthalpy change, and specific heat of the compounds were obtained using modulated differential scanning calorimetry. It was observed that the phase transition temperature decreased linearly with the increase of substitution concentration.