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Solid solutions in the series Pb(ZrxTi1−x)O3 which belong to ABO3 type compounds were studied using the X-ray Rietveld technique from the tetragonal PbTiO3 end to Pb(Zr0.53 Ti0.47)O3 which is near the morphotropic phase boundary. A systematic structure analysis carried out for this series revealed that tetragonal and rhombohedral phases coexist even when Zr/Ti ratio is 40/60. Quantitative phase analysis using Rietveld method has been carried out for compositions falling in the two phase region. Substantial decrease in distortions of the BO6 octahedra has been observed for the compositions near the morphotropic phase boundary.