Rapid urbanization in China not only promotes the rapid expansion of urban population and economic agglomeration, but also causes the aggravation of haze pollution. In order to better clarify the asymmetric and nonlinear effects of urban scale and agglomeration on haze pollution, this paper quantitatively evaluates the spatial spillover effects of population size and economic agglomeration on haze pollution in 342 Chinese cities from 2001 to 2016 by using exploratory spatial data analysis (ESDA) and spatial econometric model. The results show the following: (1) During the research period, the distribution of urban scale, agglomeration, and haze pollution in China presented complex asymmetrical features, with the former two presenting a “core–periphery” distribution mode, while the latter having a tendency to spread around. In addition, under the influence of urban population size and economic agglomeration, haze pollution in Chinese cities presents significant spatial autocorrelation, with the agglomeration degrees showing a fluctuating upward trend during the study period. (2) Both urban scale and urban agglomeration have positive global spatiotemporal correlation with haze pollution. Local spatial correlation features are more obvious in China’s emerging urban agglomerations like Beijing–Tianjin–Hebei and Yangtze River Delta. (3) The spatial effects of haze pollution are better evaluated by spatial Durbin model (SDM) with spatial fixed effects, obtaining a coefficient of 0.416, indicating haze in neighboring cities affected each other and had significant spillover. By decomposing the effect of urban scale and agglomeration on haze as direct and indirect effects, the direct effect of urban population size and the indirect effect of urban economic agglomeration are found to be more prominent, reflecting that significant asymmetrical characteristics exist in the spatial effects of urban size and agglomeration on urban haze. (4) Among the control variables that affect China’s rapid urbanization, the level of urban economic development has a positive effect on haze pollution, while the high-level industrial structure and improved technical level can effectively reduce haze pollution. Continuous decline of haze concentration of Chinese cities in recent years has been indicating the spatial relationships between haze and urban size and agglomeration have a decoupling trend. The findings contribute to theory by emphasizing the spillover effect and spatial heterogeneities of geographical factors, and have implications for policy makers to deal with haze pollution reasonably and effectively.