Air pollution fluctuations have been found to strongly depend on the weather dynamics. Here we identify the significant atmospheric processes that affect the local daily variability of air pollution. We develop a multilayered network analysis to detect the interlinks between the 500-hPa geopotential height and surface air pollution in both China and the United States. We find that Rossby waves significantly affect air pollution fluctuations through the development of cyclone and anticyclone systems and further affect the local stability of the air and the winds. Some of these systems are remote (∼3,000 km) and lead to air pollution 1–2 days later. Thus, the impact of Rossby waves on human life is greater than previously believed. The rapid warming of the Arctic could slow down Rossby waves, thus increasing human health risks. Our method can help to determine the risk assessment of such extreme events and can improve potential predictability.