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Under the background of global warming, occurrence of heat waves has increased in most part of Europe, Asia and Australia along with enhanced ozone level. In this paper, observational air temperature and surface ozone in the Yangtze River Delta (YRD) region of China during summer of 2013, and the regional chemistry-climate model (RegCM-CHEM4) were applied to explore the relationship between heat wave and elevated ground-level ozone. Observations indicated that YRD experienced severe heat waves with maximum temperature up to 41.1 °C, 6.1 °C higher than the definition of heat wave in China, and can last for as long as 27 days. Maximum ozone reached 160.5 ppb, exceeding the national air quality standard (secondary level) as 74.7 ppb. Moreover, ozone was found to increase at a rate of 4–5 ppb K − 1 within the temperature range of 28–38 °C, but decrease by a rate of − 1.3 ~ − 1.7 ppb K − 1 under extremely high temperature. A typical heat wave case (HW: 24/7–31/7) and non-heat wave case (NHW: 5/6–12/6) were selected to investigate the mechanism between heavy ozone and heat waves. It was found that chemical reactions play the most important role in ozone formation during HW days, which result in 12 ppb ozone enhancement compared to NHW days. Chemical formation of ozone can be influenced by several factors. During heat waves, a more stagnant condition, controlled by anti-cyclone with sink airflow, led to less water vapor in YRD from south and contributed to less cloud cover, which favored a strong solar radiation environment and ozone significantly increasing. High temperature also slightly promote the effect of vertical turbulence and horizontal advection, which beneficial to ozone remove, but the magnitude is much smaller than chemical effect. Our study suggests that the chemical reaction will potentially lead to substantial elevated ozone in a warmer climate, which should be taken into account in future ozone related issues. [ABSTRACT FROM AUTHOR]