Organic soil is an important transient reservoir of mercury (Hg) in terrestrial ecosystems, but the fate of deposited Hg in organic forest soil is poorly understood. To understand the dynamic changes of deposited Hg on forest floor, the composition of stable Hg and carbon (C) isotopes in decomposing litters and organic soil layer was measured to construct the 500 year history of postdepositional Hg transformation in a subtropical evergreen broad-leaf forest in Southwest China. Using the observational data and a multiprocess isotope model, the contributions of microbial reduction, photoreduction, and dark reduction mediated by organic matter to the isotopic transition were estimated. Microbial reduction and photoreduction play a dominant role in the initial litter decomposition during first 2 years. Dark redox reactions mediated by organic matter become the predominant process in the subsequent 420 years. After that, the values of Hg mass dependent fractionation (MDF), mass independent fractionation (MIF), and Δ199Hg/Δ201Hg ratio do not change significantly, indicating sequestration and immobilization of Hg in soil. The linear correlations between the isotopic signatures of Hg and C suggest that postdepositional transformation of Hg is closely linked to the fate of natural organic matter (NOM). Our findings are consistent with the abiotic dark reduction driven by nuclear volume effect reported in boreal and tropical forests. We recommend that the dark reduction process be incorporated in future model assessment of the global Hg biogeochemical cycle.