The issue of global change is getting the attention of the world. The carbon dioxide emissions produced by the fossil energy consumption is the main reason of global change. Driven by the export policy, China has become the biggest exporter and also the largest carbon dioxide emitter in the world due to the large share of energy resources in the export structure. This larger share of energy resources in export structure severely restricts the sustainable development of China. The export structure with low emissions and high added value is required for regional sustainable development. As the implementation of carbon dioxide emissions reduction in each province, it should be noted that how to achieve the best goal in the whole nation through the regional structural adjustment. Most previous studies on export structure optimization focused only on national scale. In order to reflect the export structure optimization in different regions under the constrains of low carbon and less pollution, this paper constructed a multi-regional optimization model by combining linear programming with multi- regional input- output analysis, and the export structure optimizations in China's eight economic regions in 2007 and 2010 were studied under the constrains of constant carbon and industrial pollution emissions. The results show that increasing the ratios of service and agriculture in the export structure will contribute to the environment, but it is contrary for the sector of coal mining, washing and processing, the sector of paper and products, printing and record medium reproduction, the sector of metals smelting and pressing, and the sector of electricity and heating power production and supply. It should focus on decreasing the ratios of sectors with high energy consumption and high pollution in northeast region, mid-Yellow River region, mid-Yangtze River region, southwest region and northwest region of the mainland of China, while it should focus on increasing the ratios of manufacturing and services in eastern coastal region, southern coastal region and northern soastal region. The degrees of export structure optimization in eastern coastal region, southern coastal region and northwest region were higher in 2010 than in 2007. The degrees of export structure optimization in the eastern coastal region and the southern coastal region were on top of the list. In contrast, the degree of export structure optimization in northeast region was at the bottom of the list.