The last 10 years witnessed the emerging and growing up of inductively coupled plasma mass spectrometry (ICPMS)-based immunoassay. Its high sensitivity and multiplex potential have made ICPMS a revolutionary technique for bioanalyte quantification after element-tagged immunoassay. This review focuses on the major developments and the applications of ICPMS-based immunoassay, with emphasis on methodological innovations. The ICPMS-based immunoassay with elemental tags of metal ions, nanoparticles, and metal containing polymers was discussed in detail. The recent development of multiplex assay, mass cytometry, suspension array, and surface analysis demonstrated the versatility and great potential of this technique. ICPMS-based immunoassay has become one of the key methods in bioanalysis.