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In this research, hydride generation in HPLC-ICPMS for the selenium speciation was investigated. Chemical and photochemical vapor generation techniques were compared for the effective generation of selenium vapour. HBr/KBrO3 was used for the chemical reduction and a UV lamp was used for the photochemical reduction. It was found out that the photochemical reduction was more effective than the chemical reduction in all of selenium species studied. The optimum conditions for the generation of vapour are 0.4% KI, 2.5%NaBH4, and 1.0 M HCl. The enhancement factor using a photochemical hydride generation was from 6.3 to 16.7 times for inorganic and organic selenium species.