The solid solutions of PbHfxTi1 - xO3 were synthesized by the oxidant-peroxo method in the titanium rich region (x ≤ 0.5). Lattice parameters at room temperature were investigated as a function of x by means of powder X-ray diffraction and Rietveld analysis. The phase transition between the room-temperature tetragonal to the high-temperature cubic phase was studied by DSC and dielectric measurement. Phase transitions detected in both experiments were shifted to low temperatures and smeared with increasing x. The effects of Hf/Ti substitution on PbTiO3 were compared with those of Zr/Tifor samples prepared by the same way. It was clarified that the lattice constant c and the phase transition were more sensitive to Hf content than to Zr content.