The impact of surface ozone pollution on the yield of winter wheat is empirically estimated by considering socio-economic and climatic determinants. This research is the first to use an economic framework to estimate the ozone impact, and a unique county-level panel is employed to examine the impact of the increase of surface ozone concentration on the productivity of winter wheat. In general, the increment of surface ozone concentration during the ozone-sensitive period of winter wheat is found harmful to its yield, and the damage to China’s grain supply and economic values are non-negligible. This study also confirms that other stress conditions, such as drought and air particles, can potentially mitigate the adverse effect of surface ozone exposure on the yield of winter wheat.