In the present article, the ordinary printing paper was immerged in the aqueous solution of CuCl2, and used as an absorber for the enrichment of heavy metal copper in liquid, After being taken from the solution and dried, the paper was then analyzed using laser-induced breakdown spectroscopy. This method overcomes the drawbacks of splashing and low sensitivity in the process of direct analysis of heavy metal in water sample with LIBS. The Cu 324.7 nm spectral line was used as the analysis line in experiment. The variation in the line intensity at different enrichment time was studied. The calibration curve for the quantitative measurement of Cu in water was established, the detection limit was 0.023 mg·L-1, which is about three orders of magnitude improvement compared with that in ordinary LIBS analysis of heavy metal in solution. It is likely that this technique will be practically helpful in the sensitive analysis of the heavy metal in water.