Metal-dithiocarbamate complexes are amenable to separation by chromatography and subsequent detection by atomic absorption spectrometry, u.v.-visible spectrophotometry or electroanalytical methods. Three methods of complex formation are investigated for pyrrolidinedithiocarbamate and diethyldithiocarbamate: direct formation in a solvent suitable for subsequent chromatographic separation; liquid-liquid extraction and removal of co-extracted ligand to minimize possible interferences observed with some detection methods; and precolumn formation in which the complex is deposited onto a Sep-Pak cartridge and then eluted in a solvent suitable for chromatography. Each of the methods is examined with respect to simplicity of operation, concentration factors and amenability to combination with liquid chromatography. Generally, precolumn formation of the complex is to be preferred. These methods are successfully applied to determinations of copper, nickel, cobalt, lead, mercury, cadmium, selenium, chromium(III) and chromium(VI) at the μg l-1 level.