A composite microbial system (XDC-2) was used to pretreat and hydrolyze corn stalk to enhance anaerobic digestion. The results of pretreatment indicated that sCOD concentrations of hydrolysate were highest (8,233 mg/l) at the fifth day. XDC-2 efficiently degraded the corn stalk by nearly 45%, decreasing the cellulose content by 22.7% and the hemicellulose content by 74.1%. Total levels of volatile products peaked on the fifth day. The six major compounds present were ethanol (0.29 g/l), acetic acid (0.55 g/l), 1,2-ethanediol (0.49 g/l), propionic acid (0.15 g/l), butyric acid (0.22 g/l), and glycerine (2.48 g/l). The results of anaerobic digestion showed that corn stalks treated by XDC-2 produced 68.3% more total biogas and 87.9% more total methane than untreated controls. The technical digestion time for the treated corn stalks was 35.7% shorter than without treatment. The composite microbial system pretreatment could be a cost-effective and environmentally friendly microbial method for efficient biological conversion of corn stalk into bioenergy.