Extreme air pollution meteorological events, such as heat waves, temperature inversions and atmospheric stagnation episodes, can significantly affect air quality. Based on observational data, we have analyzed the long-term evolution of extreme air pollution meteorology on the global scale and their potential impacts on air quality, especially the high pollution episodes. We have identified significant increasing trends for the occurrences of extreme air pollution meteorological events in the past six decades, especially over the continental regions. Statistical analysis combining air quality data and meteorological data further indicates strong sensitivities of air quality (including both average air pollutant concentrations and high pollution episodes) to extreme meteorological events. For example, we find that in the United States the probability of severe ozone pollution when there are heat waves could be up to seven times of the average probability during summertime, while temperature inversions in wintertime could enhance the probability of severe particulate matter pollution by more than a factor of two. We have also identified significant seasonal and spatial variations in the sensitivity of air quality to extreme air pollution meteorology.