Taking mixed agricultural organic wastes cattle manure and rice straw (C:N = 28.7:1) as the substrate of earthworm Eisenia foetida, an experiment was conducted to study the effects of earthworm on the changes of the chemical and biological properties of wastes during vermi-composting. After 30 days of vermi-composting, the substrate' s pH and C/N decreased while the total P content increased significantly, and the total N, available N, dissolved organic carbon, available P content, microbial biomass-C, respiration rate, and microbial quotient increased by 8.5% , 2.6%, 1.8%, 6.3%, 21.2%, 4.4%, and 30.0% whereas the organic matter content and metabolic quotient decreased by 5.0% and 21.9%, respectively, as compared with natural composting. Vermi-composting made the substrate have higher invertase, acid phosphatase, and alkaline phosphatase activities but lower catalase and urease activities. Principal component analysis and discriminant analysis confirmed the significant differences in the substrate' s chemical and biological properties between vermi-composting and natural composting. This study indicated that vermi-composting was superior to natural composting, which could obviously improve the chemical and biological properties of composted organic materials, being a high efficient technology for the management of agricultural organic wastes.