Normal maize starch and high-amylose maize starch were served as modal materials to prepare starch/polyvinyl alcohol (PVA) blends, respectively. The processes of anaerobic degradation were investigated in detail by evolutions of gas production, pH value in reactors, the potential of biogas-production, the energy conversion efficiency as well as the changes of film structures and compositions, to further understand the influence of the two native starches on biogas production. The results indicated that both of the films had good biodegradabilities in anaerobic condition and comparative potential of biogas-production. Nonetheless, the structure of high-amylose maize starch/PVA film was more suitable and beneficial to the anaerobic biodegradation than the normal maize starch/PVA film, because it could effectively avoid accumulation of volatile fatty acids, which contributed to the stable biogas production, 〖JP2〗short fermentation period, non souring in the reactor and higher energy conversion efficiency. Based on the agricultural film yield per year and biogas production of starch film, the corresponding energy production of high amylose maize starch/PVA film and normal maize starch/PVA film were 3.31×10 5GJ/a and 3.18×10 5GJ/a, respectively. It suggested that the starch film is a potential material for anaerobic digestion.