© 2018 by the authors. Poor air quality is often associated with hot weather, but the quantitative attribution of high temperatures on air quality remains unclear. In this study, the effect of elevated temperatures on air quality is investigated in Greater Sydney using January 2013, a period of extreme heat during which temperatures at times exceeded 40 °C, as a case study. Using observations from 17 measurement sites and the Weather Research and Forecasting Chemistry (WRF-Chem) model, we analyse the effect of elevated temperatures on ozone in Sydney by running a number of sensitivity studies in which: (1) the model is run with biogenic emissions generated by MEGAN and separately run with monthly average Model of Emissions of Gases and Aerosols from Nature ( MEGAN) biogenic emissions (for January 2013); (2) the model results from the standard run are compared with those in which average temperatures (for January 2013) are only applied to the chemistry; (3) the model is run using both averaged biogenic emissions and temperatures; and (4 and 5) the model is run with half and zero biogenic emissions. The results show that the impact on simulated ozone through the effect of temperature on reaction rates is similar to the impact via the effect of temperature on biogenic emissions and the relative impacts are largely additive when compared to the run in which both are averaged. When averaged across 17 sites in Greater Sydney, the differences between ozone simulated under standard and averaged model conditions are as high as 16 ppbv. Removing biogenic emissions in the model has the effect of removing all simulated ozone episodes during extreme heat periods, highlighting the important role of biogenic emissions in Australia, where Eucalypts are a key biogenic source.