This study examined the kinetics of photoreduction of Hg(II) and photodemethylation of methylmercury (MeHg⁺) attached to, or in the presence of, dissolved organic matter (DOM). Both Hg(II) and MeHg⁺ are principally bound to reduced sulfur groups associated with DOM in many freshwater systems. We propose that a direct photolysis mechanism is plausible for reduction of Hg(II) bound to reduced sulfur groups on DOM while an indirect mechanism is supported for photodemethylation of MeHg⁺ bound to DOM. UV spectra of Hg(II) and MeHg⁺ bound to thiol containing molecules demonstrate that the Hg(II)–S bond is capable of absorbing UV-light in the solar spectrum to a much greater extent than MeHg⁺–S bonds. Experiments with chemically distinct DOM isolates suggest that concentration of DOM matters little in the photochemistry if there are enough reduced S sites present to strongly bind MeHg⁺ and Hg(II); DOM concentration does not play a prominent role in photodemethylation other than to screen light, which was demonstrated in a field experiment in the highly colored St. Louis River where photodemethylation was not observed at depths ≥10 cm. Experiments with thiol ligands yielded slower photodegradation rates for MeHg⁺ than in experiments with DOM and thiols; rates in the presence of DOM alone were the fastest supporting an intra-DOM mechanism. Hg(II) photoreduction rates, however, were similar in experiments with only DOM, thiols plus DOM, or only thiols suggesting a direct photolysis mechanism. Quenching experiments also support the existence of an intra-DOM photodemethylation mechanism for MeHg⁺. Utilizing the difference in photodemethylation rates measured for MeHg⁺ attached to DOM or thiol ligands, the binding constant for MeHg⁺ attached to thiol groups on DOM was estimated to be 10^16.7.