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As the development of microfluidic chip and mass spectrometry, the coupling of chip with mass spectrometry (Chip-MS) has attracted increasing attention in analytical chemistry. As a miniaturized device, microfluidic chip possesses many advantages, such as reduced sample and reagent consumption, high integration, automation, etc. Using microfluidic chip to pretreat the sample can shorten the preparation time and improve the analysis efficiency. In addition, microfluidic chip can be combined with mass spectrometry for qualitive and quantitative detection, which can provide accurate information of targets and reduce the generation of false positive results. In this minireview, we summarized the fundamental developments of integrated microfluidic chip for sample pretreatment before sample introduced into MS, and the utilization of Chip-MS without liquid chromatography separation for cell metabolomics, elemental analysis, food analysis and other applications will be evaluated.