Precursor powder for the preparation of mullite was synthesized through a non-conventional semi-colloidal technique. The precursor powder was characterized by chemical analysis, DTA, measurement of surface area, bulk density and X-ray analysis. The powder was compacted with TiO2 as additive in various proportions and the sintering of the compacted masses was studied by measuring the firing shrinkage, apparent porosity, bulk density and specific gravity. The phase development and phase distribution in the sintered masses were studied by XRD and SEM. It was observed that TiO2 exhibited a positive influence on the formation of mullite from the said precursor powder at elevated temperatures. The grain size of the mullite crystals increased with the increase in TiO2 content. © 2003 Taylor and Francis Group, LLC.