Abstract: Elemental analysis of solid samples has always been the focus point of analytical chemistry. As a direct solid sampling and ionization technique, laser is often used in conjunction with time-of-flight mass spectrometry for the elemental analysis of solid samples. For the detection of high ionization potential elements, a large laser power density is often required, which results in widely dispersed kinetic energy of ions and deteriorated spectral resolution. Laser desorption/laser postionization mass spectrometry with desorption wavelength of 515 nm and postionization wavelength of 266 nm was used to detect high ionization potential elements such as Pd, Sb, Cd, and Au in this paper. On the one hand, the weak desorption laser energy greatly alleviates the problem of large kinetic energy dispersion and significantly improves the spectral resolution. On the other hand, laser postionization utilizes the “wasted” neutral atoms to improve the atomic utilization and the sensitivity of the instrument.With no sample pretreatment, this method requires short analysis time and simple operation.This method is applicable for rapid detection of high ionization potential elements in solid.