MTBE, a fuel oxygenate added to gasoline in parts of the USA, appears to have imposed significant adverse impacts on groundwater. In the UK, the impacts of MTBE are not well known in part because insufficient data has been presented to allow an accurate assessment. With the recognition of urban groundwater as a potentially valuable resource due to the growing pressure on rural groundwater, there is need for pollution risks to urban groundwater to be evaluated for contaminants such as MTBE. This paper presents the application of a risk-based water management tool called Borehole Optimisation System (BOS) in the evaluation of the risk of MTBE to urban groundwater at city scale using Nottingham city as our case study. The risk model was validated by comparison of its predictions with observations of MTBE detections for about 1100 boreholes in England and Wales. The output of the risk analysis was the production of a map showing the predicted MTBE concentration at all locations in the city. The results indicate that MTBE does not currently pose a major risk to urban groundwater although there may be a potential risk to groundwater in the southern part of the city where most industries are concentrated.