Lead isotope ratios vary depending on the origin of the lead, meaning that characteristic isotopic signatures can be used for source identification in environmental samples. Lead in ambient particulate matter was collected and analysed at 23 monitoring stations as part of the UK heavy metals air quality monitoring network to assess compliance with legislative limit values for allowable concentrations of lead in air. For the first time on a nationwide UK basis, isotopic analysis of lead was carried out on these samples to gain further information about the origin of the lead and the sources influencing measured concentrations at each of the monitoring stations. These measurements were undertaken with the novel application of ICP–MS/MS for high throughput analysis of over 200 samples from 23 sites across the UK. Values for 207Pb/206Pb ranged from 0.864 to 0.910 with an average standard error of 0.68%, while 208Pb/206Pb values ranged from 2.08 to 2.187 with an average standard error of 0.84%. The dataset was used to draw conclusions as to the main sources of pollution contributing to each site and has demonstrated the utility of ICP–MS/MS as a fit-for-purpose analytical method for the high throughput of a large number of samples in complex matrices. It was possible to identify different source types at the monitoring stations based on the lead isotope signature observed. Comparison with literature values showed clear links with traffic emissions at roadside sites and leaded petrol at a site near an airfield where small aircraft still use this type of fuel.