Constructed wetlands have the capacity to degrade a host of contaminants of emerging concern through photodegradation via sunlight produced reactive oxygen species. Dissolved organic matter (DOM) is a critical intermediary in photodegradation as it influences the production of reactive oxygen species. In this study, the photochemical behavior of DOM of wastewater treated in constructed wetlands was characterized. Whole water samples and fractionated DOM were characterized using SUVA254, spectral slope ratios, excitation emission matrix fluorescence spectroscopy (EEMs), and proton nuclear magnetic resonance (1H NMR). Photoreactivity was assessed by measuring formation rates and steady state concentrations of hydroxyl radical (•OH), singlet oxygen (1O2), and the triplet excited states of DOM (3DOM⁎). The effluent was observed to transition from a microbially sourced protein-like DOM to a terrestrial DOM with higher aromaticity. Size exclusion chromatography revealed an 18% increase in larger molecular weight fractions of vegetated wetland effluent DOM. Additionally, wetland effluent DOM was observed to have a 32% increase in the aromatic region of 1H NMR spectra as compared to untreated wastewater. 1H NMR analysis also indicated an increase in the complexity of wetland effluent DOM. Fluorescence intensity fraction of the protein-like Peak T (Ex/Em:278/342 nm) of EEMs decreased by 16% from the untreated wastewater to wetland effluent. A negative correlation between the percent fluorescence of Peak T (Ex/Em:278/342 nm) and Peaks A (Ex/Em:245/460 nm), C (Ex/Em:336/435 nm), and M (Ex/Em:312/400 nm) of the excitation emission spectra confirmed the transition from a spectrum of pure wastewater to a spectrum characteristic of terrestrially derived DOM. Microbial uptake of bio-labile DOM and leaching of humic like substances from vegetated wetland cells were the predominant processes involved in this transition. This transition coincided with an increase in the formation rates of 1O2 and 3DOM⁎ and in the steady state concentration of 1O2.