Sequential analysis of metal speciation in geological samples has been demonstrated using mass spectrometry (MS). Various speciation for metal occurrences, such as water-soluble, exchangeable, oxidable, reducible, and crystalline, have been sequentially extracted from geological samples using a homemade device, followed by online ionized for MS analysis. The metal speciation in geological samples was not only useful for revealing the formation mechanism of geological samples but also beneficial for guiding the separation and exploitation of metals. Compared with the conventional methodology, the present approach takes the advantages of short analysis time (1 h), low sample consumption (1.0 mg), and high recovery (>95%), providing a useful platform for the efficient quantitative speciation analysis of metals in geological samples. This chapter introduces the mechanism and application of the MS approach for the analysis of rare earth minerals, dinosaur fossils, soil, etc.