Increasing temperatures and more frequent heatwave events pose threats to population health, particularly in urban environments due to the urban heat island (UHI) effect. Greening, in particular planting trees, is widely discussed as a means of reducing heat exposure and associated mortality in cities. This study aims to use data from personal weather stations (PWS) across the Greater London Authority to understand how urban temperatures vary according to tree canopy coverage and estimate the heat-health impacts of London’s urban trees. Data from Netatmo PWS from 2015–2022 were cleaned, combined with official Met Office temperatures, and spatially linked to tree canopy coverage and built environment data. A generalized additive model was used to predict daily average urban temperatures under different tree canopy coverage scenarios for historical and projected future summers, and subsequent health impacts estimated. Results show areas of London with higher canopy coverage have lower urban temperatures, with average maximum daytime temperatures 0.8 °C and minimum temperatures 2.0 °C lower in the top decile versus bottom decile canopy coverage during the 2022 heatwaves. We estimate that London’s urban forest helped avoid 153 heat attributable deaths from 2015–2022 (including 16 excess deaths during the 2022 heatwaves), representing around 16% of UHI-related mortality. Increasing tree coverage 10% in-line with the London strategy would have reduced UHI-related mortality by a further 10%, while a maximal tree coverage would have reduced it 55%. By 2061–2080, under RCP8.5, we estimate that London’s current tree planting strategy can help avoid an additional 23 heat-attributable deaths a year, with maximal coverage increasing this to 131. Substantial benefits would also be seen for carbon storage and sequestration. Results of this study support increasing urban tree coverage as part of a wider public health effort to mitigate high urban temperatures.