Laser-induced breakdown spectroscopy (LIBS) is one of the most promising technologies to be applied to metallurgical composition online monitoring in these days. In order to study the spectral characters of LIBS spectrum and to investigate the quantitative analysis method of material composition under vacuum and high temperature environment, a LIBS measurement system was designed and set up which can be used for conducting experiments with high-temperature or molten samples in different vacuum environment. The system co nsists of a Q-switched Nd∶YAG laser used as the light source, lens with different focus lengths used for laser focusing and spectrum signal collecting, a spectrometer used for detecting the signal of LIBS spectrums, and a vacuum system for holding and heating the samples while supplying a vacuum environment. The vacuum was achieved and maintained by a vacuum pump and an electric induction furnace was used for heating the system. The induction coil was integrated to the vacuum system by attaching to a ceramic sealing flange. The system was installed and testified, and the results indicate that the vacuum of the system can reach 1×10－4Pa without heating, while the heating temperature could be about 1 600 ℃, the system can be used for melting metal samples such as steel and aluminum and get the LIBS spectrum of the samples at the same time. Utilizing this system, LIBS experiments were conducted using standard steel samples under different vacuum or high-temperature conditions. Results of comparison between LIBS spectrums of solid steel samples under different vacuum were achieved, and so are the spectrums of molten and solid steel samples under vacuum environment. Through data processing and theoretical analyzing of these spectrums, the initial results of those experiments are in good agreement with the results that are presently reported, which indicates that the whole system functions well and is available for molten metal LIBS experiment under vacuum environment.