The escalating issue of air pollution in China’s rapidly developing urban areas has prompted increased attention to the role of meteorological conditions in PM_2.5 pollution. This study examines the spatiotemporal distribution of PM_2.5 concentrations and their relationship with meteorological factors in six major Chinese urban agglomerations from 2017 to 2020, using daily average data. Statistical and spatial analysis techniques are employed, alongside the construction of eight machine learning models for prediction purposes. The study also compares the feature importance of various meteorological factors impacting PM_2.5 concentrations. Results reveal significant regional differences in both average PM_2.5 levels and meteorological influences. The Multilayer Perceptron (MLP) model demonstrates the highest prediction accuracy for PM_2.5 concentrations. According to the MLP model’s feature importance identification, temperature is the most significant factor affecting PM_2.5 concentrations across all urban agglomerations, while wind speed and precipitation have the least impact. Contributions from air pressure and dew point temperature, however, vary among different urban agglomerations. This research considers the impact of urban agglomerations and meteorological conditions on PM_2.5 and also offers valuable artificial intelligence-based insights into the key meteorological factors influencing PM_2.5 concentrations in diverse regions, thereby informing the development of effective air pollution control policies.