Vegetation plays a key role in the environmental cycling and fate of many organic chemicals. A compound's location on or within leaves will affect its persistence and significance; retention in surface compartments (i.e., the epicuticular wax and cuticle) renders the compound more susceptible to photodegradation and volatilization, while penetration into the epidermal cell walls or cytoplasm will enhance susceptibility to metabolism. Here, for the first time, methodologies which combine plant and PAH autofluorescence with two-photon excitation microscopy (TPEM) are used to visualize and quantify compound photodegradation on and within living plant leaves. Anthracene, fluoranthene, and phenanthrene were introduced to living leaves of Zea mays and monitored in real time, in control treatments, and when subject to UV-A radiation. Compound photodegradation was observed directly; different degradation rates occurred for different compounds (anthracene > fluoranthene > phenanthrene) and in different locations (at the leaf surface > within the epidermal cells). Results suggest that photodegradation on vegetation may be a more important loss mechanism for PAHs than previously thought. Compound fate in vegetation is potentially highly complex, influenced by diffusion into and location within leaf structures, the rates of supply/loss with the atmosphere, exposure to sunlight, and other environmental conditions. The techniques described here provide a real-time tool to advance insight into these issues.