In this paper, a Micro-Hole Array Sprayer-Assisted LIBS (MHAS-LIBS) method for liquid sample analysis was discussed. The experimental setup of this method was introduced and the stability, sensitivity and quantitative analysis properties of LIBS signal were studied. The experimental results showed that the RSD value of the spectral signal of metal elements in liquid samples was less than 2.2%. The LODs of Na, Ca, Mg and K were 0.67 mg/L, 0.29 mg/L, 0.85 mg/L, 6.18 mg/L respectively. Compared with other LIBS signal enhancement methods, the LODs of different elements were comparable or even better. The application of quantitative analysis method of MHAS-LIBS in the range of possible concentrations in sea water samples was discussed. Especially for the elements showing nonlinear characteristics, three concentration fitting methods, including the Scheibe-Lomakin function and the Cubic function, were compared. The results showed that it was a simple and practical method to fit the experimental data with the Cubic function in the target application. Finally, a quantitative method for seawater salinity determination was proposed and the estimated salinities of 5 different samples were approximately the same as the actual salinity, with a minimum error of 1.28%.