A method has been developed for on-line conversion of organoarsenicals into arsenate, which is readily detected by atomic-absorption spectrometry with continuous arsine generation. The photo-reactor consists of a mercury lamp wrapped with 5 m of PTFE tubing (0.5 mm i.d.). The photo-oxidation conditions were optimized, with a flow-injection analysis procedure, for arsenobetaine, monomethyl-arsonic acid, dimethylarsinic acid, omicron-arsanilic acid, and phenylarsonic acid, all organoarsenicals of biological and environmental importance. Solutions were continuously pumped at a flow-rate of 2.0 ml/min and combined with a stream of potassium persulfate (flow-rate 0.6 ml/min) before entering the photo-reactor. With reactor dwell times of 36 sec, conversion efficiencies for these compounds were above 95% under these conditions. Interfacing of this flow-through conversion and detection system with a chromatographic inlet permits real-time analysis of mixtures of these organoarsenic compounds, in a manner suitable for environmental or biomedical samples.