A simple and sensitive method using dithizone–chloroform single drop microextraction has been developed for separation and preconcentration of trace Cd prior to its determination by electrothermal atomic absorption spectrometry with Ir as permanent modifier. Parameters, such as pyrolysis and atomization temperature, solvent type, pH, dithizone concentration, extraction time, organic drop volume, stirring rate and sample volume were investigated. Under the optimized conditions, a detection limit (3 σ) of 0.7 ng/l and enrichment factor of 65 were achieved. The relative standard deviation was 7.4% ( c = 0.2 μg/l, n = 5). The developed method has been applied to the determination of trace Cd in water samples and biological reference materials with satisfactory results.