While the role of citizen science in engaging the public and providing large-scale datasets has been demonstrated, the nature of and potential for this science to supplement environmental monitoring efforts by government agencies has not yet been fully explored. To this end, the present study investigates the complementarity of a citizen science programme to agency monitoring of water quality. The Environment Agency (EA) is the governmental public body responsible for, among other duties, managing and monitoring water quality and water resources in England. FreshWater Watch (FWW) is a global citizen science project that supports community monitoring of freshwater quality. FWW and EA data were assessed for their spatio-temporal complementarity by comparing the geographical and seasonal coverage of nitrate (N-NO3) sampling across the River Thames catchment by the respective campaigns between spring 2013 and winter 2015. The analysis reveals that FWW citizen science-collected data complements EA data by filling in both gaps in the spatial and temporal coverage as well as gaps in waterbody type and size. In addition, partial spatio-temporal overlap in sampling efforts by the two actors is discovered, but EA sampling is found to be more consistent than FWW sampling. Statistical analyses indicate that regardless of broader geographical overlap in sampling effort, FWW sampling sites are associated with a lower stream order and water bodies of smaller surface areas than EA sampling sites. FWW also samples more still-water body sites than the EA. As a possible result of such differences in sampling tendencies, nitrate concentrations, a measure of water quality, are lower for FWW sites than EA sites. These findings strongly indicate that citizen science has clear potential to complement agency monitoring efforts by generating information on freshwater ecosystems that would otherwise be under reported.