In this work, the enzymatic saccharification of sugarcane bagasse (SCB) was enhanced after Na_2CO_3 with aqueous ammonia (NWAA) pretreatment. To achieve the highest total fermentable sugar yield (TFSY) and total fermentable sugar concentration (TFSC), NWAA parameters were optimized by response surface methodology. Under the optimum NWAA parameters, 18.16 g/L of TFSC (8.16% Na_2CO_3, 20.44% ammonia, 221.66 ℃, 1.39 h) and 0.4777 g/g of TFSY (7.21% Na_2CO_3, 20.42% ammonia, 201.92 ℃, 1.38 h) were obtained, with delignification of 94.19% and 92.80%, respectively. NWAA pretreatment significantly improved the digestibility of SCB as compared to pretreatment using Na_2CO_3 or aqueous ammonia alone. XRD, FTIR, and SEM were used for analyzing the chemical and physical characteristics of SCB samples, whose results indicated that NWAA could effectively enhance the accessibility of cellulases to celluloses. These results confirm that NWAA is a promising method for pretreatment of SCB.