Abstract: This article reviews the development and the applications of high irradiance laser ionization time-of-flight mass spectrometry（LI-TOF MS）. The critical problems in traditional high irradiance laser mass spectrometry, such as the large kinetic energy distribution of ions, multiply charged ions, polyatomic ions, matrix effect as well as fractionation effect, have been successfully solved via the new design of instrumental structure as well as the optimization of the experiment conditions. Recent applications include qualitative and semiquantitative analysis of geological and metal solids without standards, determination of nonmetallic elements, elemental imaging and depth profiling of coatings, solution residue analysis,elemental analysis of complicated biomaterial, and simultaneous acquisition of elemental, fragmental, and molecular information on organometallic compounds, which dem-onstrates the high irradiance laser ionization time-of-flight mass spectrometry as a versatile technique in analysis.