Use of nanoscale TiO2/BixMyOz (M = W, Mo) heterojunctions is one of the most promising strategies for improving the photocatalytic efficiency. However, the controllable synthesis and morphology modification of these heterojunctions are still highly challenging. In this work, we developed a generic approach to hydrothermally synthesize TiO2/BixMyOz heterojunctions and tailor their morphologies. The key to this strategy is to intentionally utilize the surface defects of TiO2 as highly active sites to adsorb the intermediate hydrolysis-products, which is in marked contrast to the conventional direct precipitation methods. In the subsequent hydrothermal reactions, MO42- replaced the hydroxyl and nitrate radicals to form stable TiO2/BixMyOz heterojunctions, in which the second phase BixMyOz occupied the defect sites of TiO2 nanobelts. Under visible light irradiation, the photocatalytic reaction rate constant of TiO2/Bi2WO6 heterojunctions was four times higher than that of single phase Bi2WO6 nanosheets, while the photocatalytic reaction rate constant of TiO2/Bi3.64Mo0.36O6.55 heterojunctions exhibited a seven-fold increase compared with Bi3.64Mo0.36O6.55 nanopaticles. The substantial enhancement of photocatalytic activity is primarily ascribed to the matching energy band structure in the TiO2/BixMyOz heterojunctions, which is able to improve the separation efficiency of photo-generated electron-hole pairs and prolong the lifetime of charge carriers in the heterojunctions.