Laser-induced breakdown spectroscopy (LIBS) shows promising applications in the analysis of environmental heavy metals. However, direct analysis in water by LIBS faces the problems of droplet splashing and laser energy decay. In this study, a novel liquid–solid conversion method based on agarose films is proposed to provide an easy-to-operate and sensitive detection of heavy metals. First, the water samples were converted into semi-solid hydrogels with the aid of agarose and then dried into agarose films to make the signal intensities stronger. The calibration curves of Cd, Pb and Cr were constructed. The proposed method was validated by standard heavy metal solutions and real water samples. The results showed that the values of R2 were 0.990, 0.989 and 0.975, and the values of the LOD were 0.011, 0.122 and 0.118 mg L−1 for Cd (I) 228.80, Pb (I) 405.78 and Cr (I) 427.48 nm, respectively. The RMSEs of validation were 0.068 (Cd), 0.107 (Pb) and 0.112 mg·L−1 (Cr), and the recovery values were in the range of 91.2–107.9%. The agarose film-based liquid–solid conversion method achieved the desired ease of operation and sensitivity of LIBS in heavy-metal detection, thereby, showing good application prospects in heavy metal monitoring of water.