In this study, the original soil pot method was used to compare the growth of three mulberry varieties in soil with excessive levels of arsenic (As) in a mining area 60 days after planting and to assess the accumulation of As in different plant parts. Metabolomics was used to analyze the characteristics of root exudates, and the As content in the rhizosphere soil was determined. A total of 296 types of root exudate were detected, and nine compounds were not secreted. G62 has a strong ability to adapt and enrich As, and its root system secretes significantly higher amounts of various organic acids, sugars, nucleosides, and their derivatives than G12 and Y120. The stress caused by soil from waste dumps significantly induced G62 roots to secrete the organic acids, sugars, amino acids, and nucleosides, which could aid G62 to better adapt and enrich As in soil from waste dumps.