In this paper, laser-induced breakdown spectroscopy (LIBS) using micro-droplet NaCl solution and set-up for control of micro-droplets are described. Micro-droplets controlling technique is important for solution quantitative analysis. In this study, micro-droplet ejection system for sampling is designed and presented. This micro-droplet ejection system enable a constant volume of the sample liquid to be obtained and it takes advantage of the liquid physical state; the density of the solution can be controlled accurately. The method presented here generates small droplets (diameter 30 μm) by confining the entire volume of the sample material in the laser beam spot area (minimum beam spot diameter: 53.2 μm) and separating it from its surroundings. Using this liquid micronizing method, improved sensitivities are obtained. The Advantage of LIBS is a useful method for determining the elemental composition of various materials regardless of their physical state (solid, liquid, or gas) and without any preprocessing; it is a type of atomic emission spectroscopy (AES). Despite the advantage of qualitative analysis, quantitative analysis is difficult because of sample and plasma fluctuations. Generating constant volume of micro-size sample and proper sample control technique contribute to LIBS quantitative analysis.