The laser-induced breakdown spectroscopy (LIBS) technique is a fast, non-contact method with no need for any sample preparation, and can be carried out under various atmospheric conditions. These properties make LIBS applicable to process control in metallurgy. In the present paper, a series of high alloy steel GBW01605-01609 samples were determined by laser induced plasma spectroscopy, based on a Nd : YAG Q-switched solid laser with wavelength 1 064 nm as an excitation source and CCD as detector. Experimental study on the interaction between laser and high alloy steel samples was completed. The effects on LIBS in high alloy steel such as observation distance and laser power density were systematically studied. The time-resolved spectrum of LIBS was also investigated. The optimum experiment conditions for the application of LIBS to the trace analysis in high alloy steel were obtained firstly.