The present paper is focused on solvent extraction of hazardous Cd(II) from acidic chloride media by Cyanex 921, a new extractant mixed with 10% (v/v) TBP in xylene. The optimum conditions for extraction and stripping of Cd(II) were investigated with an aqueous feed of 0.1 mol/L Cd(II) in 2.0 mol/L HCl. McCabe-Thiele diagram was in good agreement with the simulation studies, showing the quantitative extraction (99.9%) of Cd(II) within two counter-current stages utilizing 0.30 mol/L Cyanex 921 at O/A ratio of 3/2 in 10 min. Stoichiometry of the complexes extracted was determined and confirmed by numerical treatment and graphical method, revealing the formation of HCdCl3 center dot 2L and HCdCl3 center dot 4L for Cyanex 921(L) concentration in the range 0.03-0.1 mol/L and 0.1-1.0 mol/L, respectively. The thermodynamic parameters for the extraction of cadmium were also determined. The stripping efficiency of cadmium from the loaded organic with 0.10 mol/L HCl was 99.6% in a three-stage counter-current process at an O/A ratio of 2/3. Cyanex 921 was successfully applied for the separation of Cd(II) from Ni(II) in the simulated leach liquor of spent Ni-Cd batteries. The study demonstrates the applicability of the present hydrometallurgical approach for the treatment of hazardous waste, the spent Ni-Cd batteries. (C) 2014 Elsevier B.V. All rights reserved.