Abstract: Capillary electrophoresis-mass spectrometry (CE-MS), developed on the basis of liquid chromatography-mass spectrometry, is a new hyphenated technique that combines the advantages like high separation efficiency, short analytical time, low sample consumption in CE and the high sensitivity, powerful molecular structure elucidation in MS. It has been paid great attention by analytical scientists and become a powerful tool for analysis of active components in Chinese medicine, in vivo drugs and bio-samples like amino acids, peptides, proteins and polysaccharides. In this paper, a brief review was given on recent advance in CE-MS and its applications, including advance in sheath-flow and sheathless nano-spray interfaces and applications in analysis of pharmaceutical and biological samples. The first part of this review summarizes the development of stable and efficient interfaces to improve the feasibility of CE-MS technique. Several interfaces like coaxial sheath-flow, electrokinetic sheath-flow, liquid injection and sheathless interface with etching emitter have been reviewed. The second part introduces the application of CE-MS in the past few years. The applications are categorized according to the types of analytes, including the analysis for active components in Chinese medicines, in vivo drugs, amino acids, peptides, proteins and carbohydrates. Coatings for capillary inner wall, online processing strategies, sample preparation methods and other experiment methods have been discussed in each category. In the last part of this review, a perspective of this technique has been discussed.