Poplar processing residues were used for methane production by anaerobic digestion after alkaline treatment and methane production was measured. The highest methane production of 271.9 L/kg volatile solid (VS) was obtained at conditions of 35 g/L and 5.0% NaOH, which was 113.8% higher than non-alkaline treated samples, and 28.9% higher than that of corn straw, which is the conventional anaerobic digestion material in China. The maximal enhancement of 275.5% obtained at conditions of 50 g/L and 7.0% NaOH. Degradation of cellulose, hemicellulose and lignin after treatment increased by 4.0–9.0%, 3.3–6.2%, and 11.1–20.5%, respectively, with NaOH dose ranged from 3.0% to 7.0%. Scanning electron microscopy (SEM), FTIR spectra and Crystallinity measurements showed that the lignocellulosic structures were disrupted by NaOH. The results indicate poplar processing residues might be an efficient substrate for methane production after alkaline treatment.