The different physicochemical properties of various agro-waste biomasses require a diversity of bioenergy utilization patterns. This study investigated the characteristics of a total of 74 manures and 78 crop straw samples from East China to identify the primary characteristic indicators that are essential to distinguish specific agro-wastes from others. Principal component analysis was applied, to discover critical features of biomass for the decision-making regarding the bioenergy production mode. The results identified the following four principal components of manures: "organic nutrients", "metals", "bioavailability of nutrients", and "toxic potential". For crop straws these were "lignocellulose/plant strength elements", "organics/inorganic metals for chlorophyll", "C/N", and "Na/Zn/fixed C". Considering the practical application significance of anaerobic digestion (AD) in the ecological civilization construction in rural China, the theoretical bio-methane potential was calculated based on the average values of different agro-biomasses from different areas. The results were 335.5-620.4 STP mL/g VS for manures and 434.0-540.3 STP mL/g VS for crop straws.