The aim of this study was to determine the effect of sodium hydroxide pretreatment on the chemical composition and the methane production of ensiled sorghum forage and wheat straw. NaOH pretreatment was conducted in closed bottles, at 40 °C for 24 h. Samples were soaked in a NaOH solution at different dosages (expressed in terms of total solids (TS) content) of 1 and 10% gNaOH/gTS, with a TS concentration of 160 gTS/L. At the highest NaOH dosage the reduction of cellulose, hemicelluloses and lignin was 31, 66 and 44%, and 13, 45 and 3% for sorghum and wheat straw, respectively. The concentration of soluble chemical oxygen demand (CODs) in the liquid phase after the pretreatment was also improved both for wheat straw and sorghum (up to 24 and 33%, respectively). Total sugars content increased up to five times at 10% gNaOH/gTS with respect to control samples, suggesting that NaOH pretreatment improves the hydrolysis of cellulose and hemicelluloses. The Biochemical Methane Potential (BMP) tests showed that the NaOH pretreatment favoured the anaerobic degradability of both substrates. At 1 and 10% NaOH dosages, the methane production increased from 14 to 31% for ensiled sorghum forage and from 17 to 47% for wheat straw. The first order kinetic constant increased up to 65% for sorghum and up to 163% for wheat straw.