Laser-induced breakdown spectroscopy (LIBS), combined with a flow-injection system, is demonstrated to analyze liquid droplets of aluminum salt, as generated with an electrospray ionization device. The spray needle also serves as the anode, through which the analyte solution is spread toward the other metal base as the cathode. Along the passage of the FI manifold, the Al-sample loading speed is controlled at 0.15 mL min(-1), restricted to the small diameter of the spray needle, and the loading volume amounts to 0.1 mL. The metal ion is retained in a cation-exchange resin microcolumn immobilized with Chromotrope 2B chelating agent, followed by elution with a 0.5 M HCl solution into LIBS. Upon laser irradiation at the preconcentrated liquid droplets, the time-resolved laser-induced breakdown (LIB) emission and plasma-induced current signals are acquired concurrently on a single-shot basis. The area under the LIB/current distribution increases in linear proportion as the concentration of the sample solution increases. The detection limit thus obtained can reach 1.5 mg L(-1), about an order of magnitude lower than those achieved previously using single-laser ablation without involvement of preconcentration. The linear dynamic range is more than two orders of magnitude.