A new method for the simultaneous qualitative and quantitative determination of alkyl benzyl and dialkyl quaternary ammonium compounds (QACs) has been developed. Analysis is by reversed-phase high-performance liquid chromatography coupled with electrospray ionisation mass spectrometry. QACs are extremely amenable to the electrospray ionisation technique (limit of detection of BAC C12 homologue 3 ng ml(-1)). The selectivity of mass spectrometric detection allows simultaneous determination of benzyl and dialkyl dimethyl ammonium compounds. The method was successfully applied to the analysis of real samples (occupational hygiene sampling devices, products and swimming pool water). Structural information was obtained by MS-MS and cone voltage ion dissociation techniques. Ion dissociation enabled the structural elucidation of an unknown quaternary ammonium compound present in a commercial formulation.