Indoor air pollution (IAP) from household use of biomass and coal is a leading environmental health risk in many developing nations. Much of the initial research on household energy technology overlooked the complex interactions of technological, behavioral, economic, and infrastructural factors that determine the success of environmental health interventions. Consequently, despite enormous interest in reducing the large and inequitable risks associated with household energy use in international development and global health, there is limited empirical research to form the basis for design and delivery of effective interventions. We used data from four poor provinces in China (Gansu, Guizhou, Inner Mongolia, and Shaanxi) to examine the linkages among technology, user knowledge and behavior, and access and infrastructure in exposure to IAP from household energy use. We conclude that broad health risk education is insufficient for successful risk mitigation when exposure behaviors are closely linked to day-to-day activities of households such as cooking and heating, or have other welfare implications, and hence cannot be simply stopped. Rather, there should be emphasis on the economic and infrastructure determinants of access to technology, as well as the details of behaviors that affect exposure. Better understanding of technology-behavior interface would also allow designing technological interventions that account for, and are robust to, behavioral factors or to provide individuals and households with alternative behaviors. Based on the analysis, we present technological and behavioral interventions for these four Chinese provinces.