Air pollution spillover can cause air pollution to negatively affect neighboring regions. The structure of air pollution spillover varies with changes in season and space. Researching the spatial and seasonal characteristics of air pollution spillover is beneficial for determining air pollution prevention and control policies. First, this paper uses the GARCH-BEKK model to correlate the air pollution spillover among cities. Second, a complex network is constructed, and cities that have stronger spillover correlations are grouped into the same region. Finally, motifs are analyzed regarding the spillover relationships among regions. This paper also compares the structure of air pollution spillover during various seasons. This study determines that every season has a core region where the air pollution spillover exits the region. The core region in the spring is western East China, in the summer it is northern East China, in the autumn it is northern East China, and in the winter it is northern North China. These regions interact with most other regions. Furthermore, in spring and winter, the phenomena of air pollution spillover between regions are stronger than those in summer and autumn. We can weaken the air pollution spillover by controlling the air pollution in core regions.