It is difficult to completely remove Cr(III) from tannery effluent by alkaline precipitation due to the abundance of strong organic ligands. Thereby, the speciation of the residual Cr after alkaline precipitation is of crucial significance to guide the selection and design of further treatment process. For the first time, we revealed the speciation of the residual Cr with the aid of comprehensive analytical techniques. Results showed that the residual Cr(III) mostly located in two size ranges, i.e. the 13-100 nm fraction and the <4 nm fraction. Combined spectral analyses demonstrated Cr(III) was coordinated by carboxyl groups or hydroxyl groups in both fractions, while the complexation by nitrogen-containing groups was excluded by the total nitrogen and UPLC-MS analysis in the two fractions, respectively. Based on the comprehensive analyses, the structures of Cr(III) complexes in both fractions were proposed. Cr(III) cross-linked the carboxyl groups from polyacrylic acid chains to form the network gel structure in the 13-100 nm fraction, while the complex structure of Cr(III) in the <4nm fraction was formed through hydroxyl-carboxyl chelation by masking agents such as tartrate and citrate. Although polyoxyethylene ether was abundantly present, it was responsible for the complexation of Cr(III) in neither fraction. (C) 2016 Elsevier B.V. All rights reserved.