Existing research has shown that both climate extremes and air pollution have adverse impacts on human health and the economy. It is worth noting that climate extremes and air pollution are not independent of each other. The complex relationship between the two needs more research. In this study, the impacts of climate extremes (extreme low temperature, extreme high temperature, extreme rainfall, and extreme drought) on ambient air pollution are assessed ex post using a multiple regression analysis. Based on data from 223 Chinese cities between 2007 and 2020, our analysis generates three findings. (1) Climate extremes lead to poorer air quality by significantly increasing the concentrations of black carbon (BC), nitrogen dioxide (NO₂), ozone (O₃), organic carbon (OC), particulate matter less than 1 micron in size (PM₁), fine particulate matter (PM_2.5), particulate matter less than 10 microns in size (PM₁₀), and sulfur dioxide (SO₂). (2) Mechanism analyses suggest that climate extremes increase energy consumption and depress green innovation, which provides explanations for the deterioration of air pollution. (3) Although the effects of different types of climate extremes on air quality vary, in general, it is confirmed that all four types of climate extremes worsen air quality.