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Capillary zone electrophoresistandem mass spectrometry (CZE-MS/MS) has recently attracted attention as a tool for shotgun proteomics.However, its performance for this analysis has fallen far below that of reversed phase liquid chromatography (RPLC)-MS/MS.Here, we report the use of a CZE method with a wide separation window (up to 90 min) and high peak capacity (~300).This method is coupled to an Orbitrap Fusion mass spectrometer via an electro-kinetically pumped sheath flow interface for analysis of complex proteome digests.Singleshot CZE-MS/MS identified over 10,000 peptides and 2,100 proteins from a HeLa cell proteome digest in ~100 min.This performance is nearly an order of magnitude superior to earlier CZE studies and is within a factor of 2 to 4 of stateof-the-art nano ultrahigh pressure LC systems.