A simple chemical route is developed to obtain an important molecular precursor (leading to barium titanate powders), namely barium titanyl oxalate (BTO) with nearly theoretical yield. In this route, 0.1 M alcoholic solution of titanium tetrabutoxide is reacted with 0.1 M alcoholic solution of oxalic acid to form titanyl oxalate (TiOC2O4). This was further converted to soluble ammonium titanyl oxalate (ATO); (NH4)2TiO (C2O4)2.H2O by reacting with an equimolar aqueous solution of ammonium oxalate (pH 4.25). Instead of using available barium salts (halide/nitrate/acetate) solution, a modified barium precursor solution with controlled pH (=4.2) is prepared for carrying out cation-exchange reaction with ATO. For this purpose the modified Ba-precursor solution is freshly prepared by partial neutralization of a 0.1 M aqueous solution of barium hydroxide with controlled addition of dilute HNO3 (1.1 M) solution. The pH of this solution is the same as that of the ATO solution. The exchange reaction between equimolar ATO and modified Ba-precursor solution precipitated barium titanyl oxalate (BTO) with a quantitative yield at room temperature. Submicron-sized, stoichiometric, pure BaTiO3 powders were obtained by the controlled pyrolysis of BTO in air. The present communication deals with the detailed analysis of this simplified method in producing BTO/BT powders and their characterization employing various physicochemical techniques. © 2001 Elsevier Science Ltd. All rights reserved.