Agricultural organic wastes can leach dissolved organic matter (DOM) into surrounding water bodies, establishing them as significant sources of aquatic DOM. Given the importance of DOM in biogeochemical cycling of mercury (Hg), this DOM may mediate divalent Hg (Hg(II)) reduction, a process that remains poorly understood. This study investigated Hg(II) reduction using DOM derived from six representative agricultural wastes, categorized into livestock manure (chicken, pig, cow) and crop straw (rice, corn, rapeseed), with systematic considerations of the kinetics of reduction processes and the involvement of key free radicals. Results revealed that photoreduction was the primary pathway for Hg(II) reduction, with pig manure DOM exhibiting the highest efficiency at 36%. Key DOM quality parameters, such as protein-like components, have been identified as critical determinants of Hg(II) photoreduction capacity. Furthermore, free radicals induced by DOM could either enhance or inhibit Hg(II) reduction capacities. Specifically, in livestock manure, the superoxide anion (O2•-)·was identified as the primary radical promoting Hg(II) photoreduction of pig manure DOM. In crop straw, hydroxyl radicals (·OH) were found to inhibit Hg(II) photoreduction, whereas O2•- promoted the Hg(II) photoreduction of rice straw DOM. These findings provide valuable insights into the role of agricultural organic wastes in biogeochemical cycling of Hg within aquatic ecosystems.