This three-year study evaluates the quantity and quality of runoff from an extensive green roof on a multistory building in Toronto. Laboratory physical, chemical, and leachate analyses of eleven commercially available green roof growing media were also undertaken to help identify the potential influence that the growing media may have on runoff chemistry. Continuous precipitation and runoff data collected over 18 months outside of the winter period indicated that the green roof discharged 63% less runoff than a neighbouring conventional modified bitumen roof. Runoff volumes from the green roof averaged 42% less than the conventional roof in April and November, and between 70 and 93% less during the summer months. Water samples were collected from both roofs during 21 rain events in 2003 and 2004 and analyzed for general chemistry (e.g., pH, total suspended solids), metals, nutrients, bacteria (n = 16), and polycyclic aromatic hydrocarbons (n = 18). Loads of most chemical variables in green roof runoff were lower than from the conventional roof. Exceptions included constituents such as calcium, magnesium, and total phosphorus, which were either naturally present in the media or were added to promote plant growth. Total phosphorus concentrations in green roof runoff were significantly higher than the conventional roof (α = 0.001), and regularly exceeded the Ontario receiving water objective (0.03 mg/L). Phosphorus concentrations fell significantly after the first year of monitoring (α = 0.001), suggesting that the nutrient is being leached from the media. Chemical analyses of green roof growing media showed that levels of most constituents were similar to or lower than typical background concentrations for agricultural soils in Ontario. However, leachate concentrations from several media exceeded receiving water standards for phosphorus, aluminum, copper, iron, and vanadium. This study highlights the importance of engineering green roof media to minimize leaching of nutrients and other contaminants while maintaining their ability to support plant growth.