Ceriporiopsis subvermispora was used to modify corn stover for improving the biodegradability and biomethane yield. Corn stover was incubated with C. subvermispora for 5-90 days then anaerobically digested. It was found that the corn stover modified for 15 days achieved the highest biomethane yield of 235 mL·g-1 VS, which was an increase of 15.2% over that of the non-modified one. The mechanism analyses indicated that the improvement resulted from the combined roles of degradation selectivity, destruction of lignocellulosic structures, and linkages. The analyses showed that C. subvermispora has a high relative selectivity of lignin degradation. The structure of the lignin and the linkages among lignin and hemicellulose and cellulose were broken obviously by acetyl group removal, and the enzymatic hydrolysis of cellulose was increased by 35.61%. The finding indicated that C. subvermispora modification is one of the effective methods for enhancing biomethane yield of corn stover.