Laser induced breakdown and laser-excited atomic fluorescence spectroscopy were used to analyze trace metal atoms in water. Laser breakdown plasma was generated by a Q-switched Nd:YAG laser and an optical parametric oscillator (OPO) laser was used to excite target atoms in water. The wavelength of second laser was tuned to the absorption line of the target atom, and its time delay from the first one was optimized in order to maximize the fluorescence signal under low background light. Furthermore, the optimum transition lines were selected in terms of oscillator strength, branching ratio, and level population of target atom. In the case of Fe doped solution, the Fe concentration of less than a hundred ppb was detected. With this method, a lower detection limit of Fe was achieved than that in the case of the method using only laser-induced breakdown spectroscopy. The developed system is applicable for quick and supersensitive detection of trace metal atoms in water.