Mercury (Hg) is widely distributed in different localities around the world and poses a serious health threat to humans, especially when ingested in the form of methylmercury (MeHg). Efforts have been directed toward decreasing the production of MeHg by converting Hg to stable forms. Activated carbon and biochar have been evaluated as stabilization agents for Hg in contaminated sediments. However, the long-term fate of Hg stabilized by these materials remains unclear. Here, we compare the effectiveness of Hg stabilization using two biochars prepared from switchgrass at 300°C (lowT) and 600°C (highT). Experiments were conducted by co-blending biochars and sediment for >600 d under anaerobic conditions. Aqueous concentrations of total Hg and MeHg were greatly reduced in the presence of biochars, with the exception of a spike in MeHg concentration observed at 440 d in the high-T biochar system. Hg co-occurs with S, Fe, Cu, and other elements within the plant structure of low-T biochar particles, but primarily on the outer surfaces of high-T biochar particles. Our results indicate that the stabilization of Hg may be through an early-stage diagenetic process, suggesting that the stabilization of Hg by biochar may be effective over long time frames.