On 17th February 2003, a congestion charging scheme (CCS), operating Monday-Friday, 07:00-18:00, was introduced in central London along with a programme of traffic management measures. We investigated the potential impact of the introduction of the CCS on measured pollutant concentrations (oxides of nitrogen (NOX, NO and NO2), particles with a median diameter less than 10 microns (PM10), carbon monoxide (CO) and ozone (O3)) measured at roadside and background monitoring sites across Greater London. Temporal changes in pollution concentrations within the congestion charging zone were compared to changes, over the same time period, at monitors unlikely to be affected by the CCS (the control zone) and in the boundary zone between the two. Similar analyses were done for CCS hours during weekends (when the CCS was not operating). Based on the single roadside monitor with the CCS Zone, it was not possible to identify any relative changes in pollution concentrations associated with the introduction of the scheme. However, using background monitors, there was good evidence for a decrease in NO and increases in NO2 and O3 relative to the control zone. There was little change in background concentrations of NOX. There was also evidence of relative reductions in PM10 and CO. Similar changes were observed during the same hours in weekends when the scheme was not operating. The causal attribution of these changes to the CCS per se is not appropriate since the scheme was introduced concurrently with other traffic and emissions interventions which might have had a more concentrated effect in central London. This study provides important pointers for study design and data requirements for the evaluation of similar schemes in terms of air quality. It also shows that results may be unexpected and that the overall effect on toxicity may not be entirely favourable. © 2009 Elsevier Ltd. All rights reserved.