In order to reveal the water-rock interaction process of high arsenic groundwater formation and transportation in the western of Jilin Province, the authors used the experimental data to analyze the groundwater chemical features and high arsenic groundwater distribution in horizontal and vertical direction. By application of the PHREEQC, inverse modeling of the high arsenic groundwater was carried out. Based on the simulation, the minerals dissolution or resolution of arsenic, iron and manganese were calculated under different flow paths. The result shows that arsenic is related to them and enriched in the alkaline and reduction environment.