Recent analyses of ice core methane concentrations suggested that methane emissions from wetlands were the primary driver for prehistoric changes in atmospheric methane. However, these interpretations conflict as to the location of wetlands, magnitude of emissions, and the environmental controls on methane oxidation. The flux of other reactive trace gases to the atmosphere also controls apparent atmospheric methane concentrations because these compounds compete for the hydroxyl radical (OH), which is the primary atmospheric sink for methane. In a series of linked biosphere‐atmosphere chemistry‐climate modeling experiments, we simulate the methane and biogenic volatile organic compound emissions from the terrestrial biosphere from the Last Glacial Maximum (LGM) to the present. Using a state‐of‐the‐art chemistry‐climate model, we simulate the atmospheric concentrations of methane, OH, and other reactive trace gas species. Over the past 21,000 years, methane emissions from wetlands increased slightly to the end of the Pleistocene but then decreased again, reaching levels at the preindustrial Holocene that were similar to the LGM. Global wetland area decreased by 14% from LGM to the preindustrial time. Emissions of biogenic volatile organic compounds (BVOCs), however, nearly doubled over the same period of time. Atmospheric OH burdens and methane concentrations were affected by this major change in BVOC emissions, with methane lifetimes increasing by more than 2 years from LGM to the present. We simulate a change in methane concentration of ∼385 ppb, accounting for 88% of the ∼440 ppb increase in methane concentrations observed in ice cores. Thus glacial‐interglacial changes in atmospheric methane concentrations would have been modulated by BVOC emissions. In addition, the increase in atmospheric methane concentrations since the mid‐Holocene is partly caused in our results by the increases in anthropogenic methane emissions over this period. While the interplay between BVOC and wetland methane emissions since the LGM cannot explain the entire record of ice core methane concentrations, consideration of BVOC source dynamics is central to understanding ice core methane. Rapid changes in atmospheric methane concentrations, also observed in ice cores, require further study.