Rietveld's whole powder profile fitting method based on crystal structure refinement is applied to extract the microstructure information of several polymorphic TiO2 phases grown simultaneously during high energy vibratory ball milling of anatase phase. Warren-Averbach's method of X-ray line profile analysis is also made for comparison of above results. The X-ray powder patterns of four TiO2 phases along with alpha-Al2O3 (contamination) are simulated simultaneously for the first time to fit the experimental X-ray powder patterns of multiphase materials. The structural details of monoclinic TiO2 (B) phase are also reported first time in this paper. The advantages of the present method of analysis over the other methods of X-ray line profile analysis are discussed in details. (C) 2002 Elsevier Science B.V. All rights reserved.