Dissolved organic matter (DOM) is widely present in soil environments and plays a crucial role in controlling the morphology, environmental behavior, and hazards of arsenic (As) in soil. In the Fe-rich red soil of tea plantations, the decomposition of tea tree litter complicates DOM properties, leading to more uncertain interactions between DOM, Fe, and As. This study focused on three tea plantations in Huangshan City to investigate the contents of DOM, Fe, and As in surface red soils (Ferralsols) and establish their correlations. Three-dimensional fluorescence spectroscopy and PARAFAC analysis methods were used to analyze the DOM components and fluorescence signatures. Additionally, the process and mechanism of the binding of DOM-Fe with As were explored through laboratory experiments on the morphological transformation of As by DOM-Fe. The results showed that the pH values of the soils in the three tea plantations ranged from 3.9 to 5.2, and the entire sample was strongly acidic. The DOM exhibited strong intrinsic properties and low humification, containing three types of humic acid components and one intermediate protein component. The DOC content in the Fe-rich red soil did not have a direct correlation with Fe and As, but the interaction of DOM fractions with Fe significantly influenced the As content. Specifically, the interaction of protein-like fractions with Fe had a more pronounced effect on the As content. The maximum sorption rate of As by DOM was 15.45%, and this rate increased by 49 to 75% with the participation of Fe. In the configuration of the metal electron bridge, Fe acts as a cation, forming a connecting channel between the negatively charged DOM and As, thus enhancing the DOM’s binding capacity to As. DOM-Fe compounds bind As through surface pores and functional groups. These findings provide deeper insights into the influence of DOM on As behavior in Fe-rich soil environments and offer theoretical support for controlling As pollution in red soil.