In the traditional chemical vapor generation system of KBH4 (or NaBH4)–Cd21–HCl in aqueous solution,volatile components containing cadmium species can be generated but with low efficiency. In this work, it wasfound for the first time that the efficiency for the generation of the cadmium-containing vapor was greatlyimproved when halogenate, i.e., NaBrO3 or NaIO3, was added. The chemically generated vapor was separatedfrom the reaction medium, and introduced into an atomic fluorescence spectrometer (AFS) with argon as thecarrier gas, for the atomization and detection of cadmium. The experimental conditions for the efficientgeneration of the cadmium-containing vapor were optimized and the limit of detection (LOD, 3s) was thenfound to be 10 pg mL21. This modified chemical vapor generation system is potentially cleaner, and could havewide applications for sample introduction and/or matrix separation in analytical atomic spectrometries, such asflame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS),inductively coupled plasma atomic emission spectrometry (ICP-AES), ICP-MS (mass spectrometry), microwaveinduced plasma atomic emission spectrometry (MIP-AES) and MIP-MS for the determination of ultratracecadmium or some other elements.