Emerging organic contaminants (EOCs) are chemically stable and bioaccumulative, and pose severe challenges to ecological safety and human health. On-line solid-phase extraction (SPE)-liquid chromatography (LC)-mass spectrometry (MS) is a recently developed technique for detecting EOCs in the environment. It offers the advantages of being simple, automated, low-cost, time-saving, and reducing the use of hazardous solvents. This review summarized the development of on-line SPE-LC-MS for detection of pesticides and residues, pharmaceuticals, personal care products, per- and polyfluorinated alkyl substances, and multiple-class of EOCs in the environment over the last five years, and described the limiting factors that affect the sensitivity and accuracy of on-line SPE. Finally, the application of on-line SPE-LC-MS in the detection of EOCs in different environments, such as water, atmosphere and biota, was introduced. This review also proposed that the future trend is to promote full automation and miniaturization of the whole system to fit real-time detection needs.