Increasing urbanization in China has caused severe haze pollution in Chinese cities in recent years. This study investigates the impact of urban spatial development mode on haze pollution from the leapfrog spatial dimension. We constructed a dataset containing LandScan population dynamic statistical data, PM2.5 surface concentration data, and urban economic statistical data and adopted ordinary least squares (OLS) and instrumental variable methods. The findings indicate that the polycentric spatial structure within the city increases the PM2.5 levels, indicating that the urban monocentric spatial development mode is conducive to alleviating haze pollution. The use of the core explanatory variables, lagged by one and two periods, and of the number of Qing Dynasty walls as the instrumental variable confirm the robustness of the benchmark results. The heterogeneity analysis demonstrates that, in cities with underdeveloped public rail transit, the monocentric spatial development mode has a more obvious effect on reducing haze pollution. The results of the influence mechanism test show that the urban polycentric spatial development mode aggravates urban haze pollution, mainly by encouraging residents to travel by private transport, thereby increasing energy consumption. The obtained research results provide a sufficient basis for taking appropriate measures to govern haze pollution in Chinese cities from the perspective of polycentric spatial development mode.