Soil dissolved organic matter (SDOM) has a strong complex with divalent mercury (Hg(II)) and can affect the fate of aqueous Hg(II) photoreduction. However, little is known about the influence of straw returning and soil tillage on the composition of SDOM in paddy soil and Hg(II) photoreduction in paddy water. Here, we demonstrate that the combined drivers of long-term straw returning and tillage can result in higher degrees of aromatization, and the enrichment of oxygen-containing functional groups in surface SDOM. Hg(II) photoreduction under low Hg/DOC conditions is mainly constrained by the composition of SDOM, whereas solar radiation emerged as a dominant controlling factor associated with high ratio of Hg/DOC. By increasing the release of SDOM and mobility of Hg(II), reducing the stability of Hg(II)-SDOM complexes, and potentially enhancing generation of reactive intermediates, gear effect of straw returning and soil tillage significantly enhanced Hg(II) photoreduction in the presence of surface SDOM from 0–40 cm (maximum photoreduction percentage can reach 44.76 ± 2.24 %). Previous inventories of Hg(0) emissions from paddy field system may have overlooked or underestimated this critical process. Future modeling work should be carried out to evaluate the role of straw returning and soil tillage on global Hg cycle.