Tear fluid biomonitoring represents a promising method for assessing exposures because it can be collected with minimal invasiveness and tears contain exposure markers from both the external and internal environments. Tear fluid uniquely interfaces with the external environment at the air-tear interface, providing a surface for airborne chemicals to diffuse into the ocular environment and interact with biomolecules. Tear fluid also contains molecules from the internal environment that have travelled from the blood to tears by crossing the blood-tear barrier. This review demonstrates that tear fluid can be used to identify hazardous chemicals from the external environment and differentiate exposure groups.