Groundwater environmental assessment is a useful tool for environmental planning and decision-making. Up to now, many studies have been carried out and several index models have been developed for assessing groundwater vulnerability worldwide. Because of the complicated characteristics of groundwater environmental system, however, there still has no a satisfactory methodology for the comprehensive assessment of groundwater environmental risk. In this paper, an index system, with multi-level structure, was first established for groundwater environmental risk assessment, by using twenty-two qualitative and quantitative indictors chosen from such fields as geology, hydrological geology, landform, pollution qualities, types of land use and social values of groundwater, etc. Meanwhile, the groundwater environmental risk was defined as a multiplication between grade of risk and importance of risk, and the classification standards for grade of risk and importance of risk were also primarily established, individually. On the bases, a fuzzy multi-attribute decision-making model was proposed for the assessment of groundwater environmental risk. As a case, above index system and model were utilized to evaluate the groundwater environmental risk of three cities, located in the north of Anhui Province. Study result showed that the index system and multi-attribute decision-making model established above were reasonable and effective for groundwater environmental risk assessment.