Anthropogenic mercury (Hg) emissions to the atmosphere have increased the concentration of this potent neurotoxin in terrestrial and aquatic ecosystems. The magnitude of regional variation in atmospheric Hg pollution levels raises questions about the interactions between natural processes and human activities at local and regional scales that are shaping global atmospheric Hg cycling. Peatlands are potentially valuable and widespread records of past atmospheric Hg levels that could help address these questions. This perspective aims to improve the utility of peatlands as authentic Hg archives by summarizing the processes that could affect Hg cycling in peatlands. We identify the overlooked role of peat vegetation species and their primary productivity in Hg sequestration under climatic and anthropogenic activities. We provide recommendations to improve the reliability of using peat cores to reconstruct the atmospheric Hg levels from past decades to millennia. Better information from peatland archives on regional variation in atmospheric Hg levels will be of value for testing hypotheses about the processes controlling global Hg cycling. This information can also contribute to evaluating how well international efforts under the UNEP Minamata Convention are succeeding in reducing atmospheric Hg levels and deposition in different regions.