In this work, laser-induced breakdown spectroscopy (LIBS) was applied for the detection of Pb in Tieguanyin tea and ash. Firstly, the Tieguanyin tea and ash containing Pb were prepared, and the difference of intensities of Pb I spectral lines before and after the ashing treatment was studied. It was found that the intensities of Pb I lines increased by 30 times and the standard deviation of background signal decreased by 41% after the ashing treatment. Therefore, the enrichment of Pb element by ashing treatment was used to detect Pb in tea with high sensitivity. Then, the calibration curve of Pb was established using spectral lines without self-absorption, and the determination coefficient (R2) for the linear fitting of calibration curve was 0.979 9. Finally, it was found that the limit of detection of Pb was 233.8 ppb. Compared with the results of other works which detect Pb directly, the enrichment of Pb by ashing treatment improved the detection sensitivity of Pb by about 200 times. In addition, this method can be applied to the high sensitivity detection of other heavy metals, such as Cr, Cd, Hg, etc in plants, Chinese herbal medicine, flour, rice, coal and other solid materials.