Understanding the responses of biological communities to elevated CO2 (eCO2) is a central issue in ecology, but little is known about the influence of eCO2 on the structure and functioning (and consequent feedbacks to plant productivity) of the belowground microbial community. Here, using metagenomic technologies, we showed that 10 years of field exposure of a grassland ecosystem to eCO2 dramatically altered the structure and functional potential of soil microbial communities. Total microbial and bacterial biomass were significantly increased at eCO2, but fungal biomass was unaffected. The structure of microbial communities was markedly different between ambient CO2 (aCO2) and eCO2 as indicated by detrended correspondence analysis (DCA) of gene-based pyrosequencing data and functional gene array data. While the abundance of genes involved in decomposing recalcitrant C remained unchanged, those involved in labile C degradation and C and N fixation were significantly increased under eCO2. Changes in microbial structure were significantly correlated with soil C and N contents and plant productivity. This study provides insights into potential activity of microbial community and associated feedback responses of terrestrial ecosystems to eCO2.