With the rapid improvement of China's urbanization, the new patterns of economic development based on urban network and dominated by industrial agglomeration is increasingly prominent. To this end, combining the theory of urban and environmental economics, this paper measures the polycentric spatial structure of each province by calculating the order index of city size distribution and the adjusted primacy index, and discusses the dynamic influence and mechanism of regional polycentric development mode on urban haze pollution in China by using instrumental variable estimation. The results show that the effect of polycentric space structure on urban haze pollution in China presents a significant inverted U-shaped feature, which is still stable after distinguishing city size and winter heating conditions. Meanwhile, the calculation results show that only a few provinces are in the stage where haze pollution decreases with the improvement of polycentric structure, but the haze pollution in most provinces aggravate with the increase of polycentric level. Finally, the mediating effect analysis shows that market integration and the flow of factors are important ways to improve China's haze pollution through polycentric spatial development model. Meanwhile, market integration, factor flow and polycentric spatial structure could have a significant positive synergistic effect on reducing haze pollution. The findings of this paper provide some empirical evidence and policy inspiration to consider China's future regional spatial development patterns from the perspective of haze control.