Anaerobic co-digestion of sewage sludge and corn silage with zero-valent iron powder (Fe0), cellulase, and papain as reinforcement means was conducted. COD-based feeding ratio of sewage sludge to corn silage was set to 2:1, the solids retention time (SRT) 20 day, digestion temperature 35 °C, and mixing speed 60 rpm. Removal rates of total COD during the control group, and Fe0, papain, cellulase, and papain, Fe0, and the two kinds of enzyme-added tests were 38.04, 41.02, 34.62, 34.55, 35.42, and 48.21%, respectively. The corresponding biogas production was 2.12, 2.62, 2.22, 2.41, 2.25, and 2.81 dm3/day, respectively. The results indicated the addition of cellulase, and papain could maximize the decomposition and hydrolysis of organic matter in sewage sludge and corn silage to volatile fatty acids. Fe0 could reduce the redox potentials of the anaerobic co-digestion, optimize the circumstances of the methanogenesis stage, accelerate biogas production, and improve biogas components. Fe0 and enzymes played a synergistic role in the anaerobic co-digestion system. Life cycle assessment indicated that the anaerobic co-digestion of sludge and corn silage co-substrates could benefit the economy, environment, and social development under the synergistic action of Fe0 and enzymes.