The document describes a new method for selenium speciation using HPLC coupled with atomic fluorescence spectrometry (AFS). Key aspects of the method include: 1) An online UV photolysis and UV/TiO2 photocatalysis reduction device (UV–UV/TiO2 PCRD) is used to photolyze organic selenium species and reduce selenium in high oxidation states. 2) A newly designed electrochemical vapor generation (ECVG) cell is used as an interface between HPLC and AFS, generating selenium vapor for detection. 3) The method was tested on several selenium species with detection limits of 2.1-4.3 ng/mL. It was then applied to speciate selenium in