Abstract: Along with the industrial development and human society progress, large number of pollutants have been discharged to induce the environmental pollution, which have attracted global attentions. To evaluate the environmental pollution and environmental effects, the fast, accurate, and reliable analytical methods are required for qualitative and quantitative analysis of pollutants. Ambient mass spectrometry (AMS) has the advantages of rapid, in-situ and real-time analysis of samples at ambient conditions, without any sample pretreatment. Herein, from the perspective of different ionization technologies, the applications of electrospray ionization mass spectrometry (ESI-MS), atmospheric pressure chemical ionization mass spectrometry (APCI-MS), as well as the corresponding coupling techniques for the detection of environmental water pollutants were reviewed. Finally, the development of ambient ionization mass spectrometry in the detection of environmental pollutants was summarized and prospected.