Methylmercury [MeHg(I) in the aerobic surface water of lakes is thought to be rapidly degraded, but contrary to expectations, we show that MeHg(I) concentrations often increase during sunlight hours or remain relatively constant. We hypothesized that there were water column processes that generated MeHg(I) and that these processes were linked to dissolved organic matter (DOM) and solar radiation. A 2-day diurnal pattern of MeHg(I) in surface water with corresponding bottled controls was assessed for two contrasting lakes in Kejimikujik, Nova Scotia, Canada. Following this study, a tangential ultrafiltrator was used to size-fractionate and generate a concentration gradient of DOM from four different lakes located near Lac Berthelot, Quebec, Canada. The watersheds of two of these lakes were not substantially logged whereas the other two had been extensively logged. Different size fractions of DOM as well as different concentrations of DOM were exposed to sunlight for varying periods of time. We observed that, in Keiimikujik, the concentration of MeHg(I) in surface waters peaked in the early afternoon. Furthermore, this also occurred in bottled water for one of the lakes, Puzzle, eliminating the possibility that in-lake mixing played a role in this pattern. The formation of MeHg(I) was found to be dependent on the size fraction and amount of DOM present in the water. Specifically, DOM less than 5 kDa or between 30 and 300 kDa generated MeHg(I) when exposed to sunlight, but larger fractions did not. Furthermore, although data are limited, we found that water from lakes with logged watersheds generated MeHg(I) when exposed to sunlight, whereas water from lakes with low levels of logging in the undisturbed watersheds did not. Our results demonstrate that MeHg(I) can be formed in freshwaters of certain lakes in response to solar radiation. This photoproduction of MeHg(I) is dependent on DOM concentrations and type, with the importance of water chemistry not yet clear. The significance of this process to freshwater lakes and the mechanism responsible for MeHg(I) photoproduction is still unclear, but a correction in the conventional wisdom that MeHg(I) is rapidly photodegraded is timely.