A new method has been described for generation of volatile species of Cd using vanadium(III) cyanide complex. Aqueous solutions of 0.04 mol L-1 vanadium chloride (VCl3) and 0.12 mol L-1 potassium cyanide (KCN) were reacted on-line yielding a suspension of vanadium hydroxide, V(OH)(3). This suspension was dissolved along the stream of sample solution in dilute HCl to form heptacyanovanadate(III) complex, [V(CN)(7)](4-). Volatile Cd species were generated by reacting the stream of sample solution and cyanovanadate(III) complex with sodium borohydride (NaBH4). Feasibility of off-line and on-online approaches was investigated for quantitative determinations. Better precision and daily stability were achieved with on-line settings. Optimum signals were obtained from sample solutions within a range of 3 to 5% v/v HCl. A concentration of 2% m/v NaBH4 was adequate to achieve an enhancement of 20-fold in the presence of cyanovanadate(III) complex. The limits of detection were 5.0 and 4.5 ng L-1 for Cd-110 and Cd-111 isotopes, respectively. Precision (%RSD) was better than 4.7% for six replicate measurements. The interferences of Cu(II) and Ni(II) were marginal ( < 10%) at 1.0 mu g mL(-1). Depressive effects from Bi, Se and Sn were not significant below 0.1 mu g mL(-1). The method was validated by determination of Cd using ICP-MS in certified reference materials of Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4) and Mussel tissue (SRM 2976). Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.