Vegetation supports life on Earth, from supplying oxygen to the atmosphere to playing a role in the cycling of water. However, metabolic processes in plants can also emit natural or biogenic volatile organic compounds (BVOCs). BVOCs are an important precursor to the formation of tropospheric ozone—a compound that can adversely affect air quality, human health, and the environment—yet there are many outstanding questions regarding the emission and flux of BVOCs from the forest to the atmosphere. This review synthesizes of recent research results pertaining to forest-atmosphere exchange, including the formation and fate of primary biogenic ozone precursors and the key physical and chemical processes occurring within and above vegetation canopies that control the efficient exchange of gases. Knowledge of these processes can improve our understanding of the forested environment and its role in sustainable air quality. We conclude from this review that, while we have a deep understanding of a vast array of processes that regulate BVOC emissions to the atmosphere on a local level, how those processes feedback to regional-scale air quality and climate is less understood. A synthesis of data from a wide variety of forest sites may help improve our understanding of the role of forests on air quality and climate and allow policy makers to make informed decisions with respect to maintaining sustainable air quality and climate.