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The online coupling of capillary electrophoresis (CE) with ambient direct analysis in real time mass spectrometry (DART-MS) was realized in this work.The analytes eluted from CE were directly ionized by the metastable helium flux produced by DART and transferred into MS for the detection,with which the online separation and simultaneous detection were achieved.CE-DART-MS can tolerate higher concentrations of detergents and salts than traditional CE-ESI-MS and avoided the difficulties of collecting CE effluent and cleaning the interface,which simplified the experimental procedures and shortened the analysis time.The performance of the technique were successfully verified by capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) using a mixture of 4-aminoantipyrine,zolmitriptan and quinine.This online technique showed good reproducibility and robustness.Compared with CE-ESI-MS,the ion suppression effects of non-volatile salts and detergents were efficiently minimized.The signal intensity remained constant when the concentrations reached 100 mM for sodium borate and 30 mM for SDS (in 30 mM sodium borate buffer) when MEKC was used.