Perovskite structure-based ceramic precursors have a characteristic property of substitution in the 'A' site of the ABO(3) structure. This makes them a potential material for nuclear waste management in synthetic rock (Synroc) technology. In order to simulate the mechanism of rare earth fixation in perovskite, PrxCa1-xTiO3 (where x = 0.1) has been synthesized through ceramic route by taking calculated quantities of oxides of Ca, Ti and Pr as starting materials. The ceramic phase has been characterized by its powder diffraction pattern. The Rietveld analysis of the X-ray diffraction data has been carried out using GSAS software to achieve the convergence which gives the R-p = 5.74% and R-wp = 8.17%. The (h, k, l) values for different lattice planes have been calculated. The praseodymium substituted perovskite crystallizes in orthorhombic symmetry with space group: Pbnm, Z = 4. The unit cell parameters at room temperature are a = 5.39609(31) angstrom, b = 5.44869(30) angstrom and c = 7.6565(5) angstrom. The calculated and observed values of the corresponding intensities, 2 theta and density of the polycrystalline powder show good agreement. GSAS-based calculation for bond distances Ti-O, Ca-O and bond angles O-Ti-O, O-Ca-O has been reported. (c) 2005 Elsevier Ltd. All rights reserved.