A self-mode lab’s high sensitive atomic fluorescence spectrometric detection system combined with liquid chromatography，online ultraviolet photochemical digesting and vapor generation device was established and evaluated.Arsenic and selenium species in various samples were extracted by heating-shaking and centrifugal filtration.All the analytes were separated on a reversed-phase column using mobile phase of 5.0 mmol/L phosphate buffer(pH 5.7)-0.5 mmol/L tetrabutyl ammonium bromide(TBAB)-1%methanol.The separations of AsO3-3，DMA，MMA，AsO3-4 and SeCys，SeMet，SeO2-3，SeO2-4 were achieved within 7 min and 11 min，respectively.Under the optimized operating conditions，the detection limits(DLs，S/N=3) were in the range of 0.08-0.74 μg/L,and the relative standard deviations(RSD，n=7) were 1.4%-7.9%.The standard spiked recoveries for real samples were in the range of 82.5%-116.5%.Linearities were obtained in the ranges of 0.28-40.0 μg/L for arsenic species and 0.38-80.0 μg/L for selenium species.The developed system was successfully applied in the detection of low levels of arsenic and selenium species in matrices.