A highly-sensitive automatic transient laser-induced breakdown spectroscopy (LIBS) system is designed and integrated. It successfully avoids the delay time selecting problem in the conventional LIBS system, and realizes the LIBS data acquisition with high spatiotemporal resolution automatically. Multiple transient spectra can be obtained in each measurement, which will provide more information for spectral research. The water-vapour and liquid-water Raman scattering spectra are captured by this system, and the comparison of experimental water-vapour Raman scattering spectrum with theoretical data verifies the reliability of the LIBS system. Based on this system, the air laser induced air breakdown spectra are captured and analysed. The system is also useful for the research on water-vapour Raman Lidar remote sensing.