In the present study, two new aqueous Cr(III)-citrate species were synthesized. The new species were characterized by elemental analysis, spectroscopic, structural, thermal, EPR and magnetic susceptibility studies. Detailed aqueous speciation studies in the Cr(III)-citrate system suggest the presence of a number of species, among which is the mononuclear [Cr(C6H5O7]23- complex, optimally present around pH ~4.0-5.0.