Ozone pollution that threatens human health and the ecosystem is a global environmental challenge. In megacities, ozone pollution has long been mainly attributed to anthropogenic sources. However, the processes and mechanisms of cross-regional transport of ozone and its precursors under interactions between mixed sources remain unclear. Here, we show that Northwest Pacific typhoons could intensify the chemical interactions between anthropogenic and biogenic emissions, resulting in extreme ozone pollution in two main city clusters in China. By integrating field and satellite observations together with model simulations, we show that biogenic emission and cross-regional ozone transport are greatly enhanced by approaching typhoons, with the increments reaching up to 78.0 and 22.5%, respectively. Ozone formation efficiency has more than doubled because of abundant precursors and active photochemistry. This study highlights the importance of natural emissions in areas with intensive human activity, which needs to be considered in future air pollution control in China.