This article reports our investigation of groundwater As in Hetao plain, Inner Mongolia. Based on field surveys, groundwater sampling, water analysis, laboratory experiments and data analysis, we found that the distribution of high As in groundwater exhibits a distinct spatial zonation. Five high As zones have been detected, including Shuangmiao-Sandaoqiao, Shahai-Manhui, Bainaobao-Langshan, Taerhu, and Shengfeng, which are coincident with subsidence center of the basin. The relationship of the distribution of high As groundwater to the paleo-geographical environment and to the groundwater environmental evolution are discussed in details.