Simultaneous vapor generation of zinc (Zn) and cadmium (Cd) was evaluated by atomic fluorescence spectrometry coupled with an intermittent flow vapor generation system. Some complexing reagents, surfactant and transition metal ions were respectively tested as enhancement reagents. Experiments showed that an appropriate amount of 8-hydroxyquinoline or phenanthroline and nickel ion simultaneously, effectively improved the vapor generation efficiency of Zn and Cd. The volatile species generation was presumed to be a hydrogenation process interpreting how the enhancement reagents played an important role in vapor generation. Additionally, due to the instability of volatile species, reaction temperature, rapid and sufficient mixing of reagents and rapid separation of the volatile species from liquid phase were also crucial. The method of simultaneous determination of Zn and Cd by intermittent flow vapor generation led to the development of atomic fluorescence spectrometry. The detection limits (3σb) were 1.6μg l−1 for Zn and 0.01μg l−1 for Cd and the relative standard deviations were 3.6% for Zn (50μg l−1, n=11) and 1.7% for Cd (2μg l−1, n=11) respectively. Results for the determination of Zn and Cd have been confirmed by the analysis of CRMs with good agreement between the certified and found values.