Abstract: The generating efficiency of solar cells is directly influenced by the varieties and contents of the impurities in solar-grade crystalline silicon, thus detecting the content and distribution of the impurities in silicon material is of great importance. The rapid development of the photovoltaic industry has promoted the development of related detection techniques. In this paper, characteristics of different types of mass spectrometric methods and their deficiencies used in silicon detection were summarized. Their principles, advantages and disadvantages of the four techniques that could use in crystalline silicon impurity detection were compared, which included the inductively coupled plasma mass spectrometry (ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS), and laser ionization mass spectrometry (LIMS).