As a fast-developing technique for in situ multi-element analysis method, laser induced breakdown spectroscopy - LIBS is, however, developing slowly on liquid analysis due to some technical difficulties. We propose a new method, namely capillary mode, to quantify the concentrations of the elements in solution using LIBS. A Nd:YAG laser with repetition of 10 Hz were used to analyze the solution of Na2CrO4 and no any sample preparation in measurements. The experimental results show that the splashing of liquid induced by laser pulses is decreased significantly and the pollution of mirrors is avoided effectively using liquid capillary mode. The results of quantitative analysis for liquid are also improved than other method. The calibration curves of Cr and Na are well characterized by straight lines and the regression coefficient values of the linear fit are better than 0.998. The limits of detection (LODs) of Cr and Na are determined to be 28.9 mg/L and 1.0 mg/L in this work, respectively. The experimental results show that the liquid capillary mode provides a more practical and very simple approach to improve accuracy of quantitative element analysis in liquids by LIBS technique.