In this study, we examine a supply-chain approach to more effectively mitigate primary PM2.5 emissions in China from the perspectives of production, consumption and their linkages using structural path analysis. We identify the pattern of all supply chain paths using principal component analysis. To address the severe haze problems in China, it is important to understand how final demand purchase initiates production processes and ultimately leads to primary PM2.5 emission. We found that consumers' demands on power and transportation mainly induce direct emissions, quite different from the demands on construction, industry and service products which largely drive emissions in upstream activities. We also found that nearly 80% of the economic sectors in China follow a similar pattern in generating primary PM2.5 emissions in electricity, cement and the ferrous metal industries; but only the construction sector increases the release of PM2.5 due to the production of non-metallic mineral products. These findings indicate that further reduction of end-of-pipe emissions in the power and transportation sectors will facilitate cleaner production in almost all the economic sectors. However, for urbanization induced emissions, China should mitigate PM2.5 emissions through the supply chain of construction, either severely reducing its life-cycle intensity or carefully planning to avoid extensive, unnecessary building activity.