A dynamic reaction cell ICP-MS was used as a CE detector for the speciation analysis of arsenic and selenium. Samples containing arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, selenite, selenate, selenocysteine, selenomethione, and Se-methylselenocysteine were subjected to electrophoretic separation before being introduced into the microconcentric nebulizer (CEI-100) for their determination by ICP-MS. The separation has been achieved in a 60 cm length x 75 microm id fused-silica capillary. The electrophoretic buffer used was 25 mmol/L CAPS, and 0.5 mmol/L SDS at pH 9.5, whereas the applied voltage was set at 25 kV. The potentially interfering (38)Ar(40)Ar(+) and (40)Ar(40)Ar(+) at the selenium masses m/z 78 and 80 were reduced in intensity by approximately three orders of magnitude by using 1.4 mL/min CH(4) as reactive cell gas in the dynamic reaction cell. Arsenic was determined as the adduct ion (75)As(12)CH(2) (+) at m/z 89. The LOD for arsenic and selenium was in the range of 0.6-1.8 ng/mL, and 0.5-1.4 ng/mL, respectively, based on peak height. This method has been applied to determine various arsenic and selenium compounds in NIST SRM 1633a Coal Fly Ash and NRCC DOLT-3 Dogfish Liver reference materials and a selenium dietary supplement. The arsenic and selenium compounds were extracted from fish liver and dietary supplement by using Protease XIV and Lipase, and from coal fly ash with HF solution. The spike recoveries were in the range 91-103% for all the species studied.