Ceramic precursors of Zirconolite (CaZrTi2O7) family have a remarkable property of substitution on Zr4+ cationic sites. This makes them potential material for nuclear waste management in 'synroc' technology. In order to simulate the mechanism of partial substitution of zirconium by tetravalent actinides, a solid phase of composition CaZr0.95U0.05Ti2O7 has been synthesized through ceramic route by taking calculated quantities of oxides of Ca, Ti and nitrates of uranium and zirconium respectively. Solid state synthesis has been carried out by repeated pelletizing and sintering the finely powdered oxide mixture in a muffle furnace at 1050 degrees C. The polycrystalline solid phase has been characterized by its typical powder diffraction pattern. Step analysis data has been used for ab initio calculation of structural parameters. The SEM and EDAX analysis also confirm that zirconolite acts as a host material for uranium. The powder diffraction data of 3500 points between 2 theta = 10 - 80 degrees has been analysed by GSAS ( general structure analysis system) software to obtain the best fit of the observed data points. The uranium substituted zirconolite crystallizes in monoclinic symmetry with space group C2/c (# 15). The following unit cell parameters have been calculated: a = 12.4883( 15), b = 7.2448( 5), c = 11.3973( 10) and beta = 100.615( 9)degrees. The calculated and observed values of the intensities, lattice parameters and density measurement shows good agreement. The Rietveld analysis and GSAS based calculations for bond distance Ti-O, Ca-O, Zr-O, and O-M-O bond angles have been made. The structure was refined to satisfactory completion. The and Rp and Rwp are found to be 7.48 and 9.74 % respectively. (C) 2005 Springer Science + Business Media, Inc.