Laser induced breakdown spectroscopy (LIBS) is a potential technique for rapid analysis of samples present in solids, gases and liquids. In the last two decades it was an object of extensive studies. Controlled calibration method used to analysis the LIBS spectra is investigated. Compared with the inner calibration and calibration-free (CF) methods, this new method overcomes “matrix effect”, and demonstrates a better ability to cope with the spectra. It is used to analyze natural soil, and errors of the concentration are decreased about 5%. The result shows that the new method is feasible and accurate.