In this work, an efficient aqueous ammonia with glycerol (AAWG) method to improve the digestibility of sugarcane bagasse (SCB) was developed. Response surface methodology was utilized to optimize the AAWG parameters to achieve the maximum total fermentable sugar concentration (TFSC) and total fermentable sugar yield (TFSY). Under optimal AAWG conditions, 13.59 g/L TFSC (9.25% ammonia, 1.86 h, 180 °C) and 0.4449 g/g TFSY (9.51% ammonia, 1.78 h, 180 °C) were achieved, with delignification of 77.81% and 70.91%, respectively. Compared to pretreatment with glycerol or aqueous ammonia, the AAWG method significantly enhanced the enzymatic efficiency of SCB. The ammonia was recovered from the pretreatment liquid by distillation, and about one-third of the ammonia was retained. The overall results indicate that AAWG is effectively used as a pretreatment method for recovering ammonia, which would largely contribute to the economic benefits of biomass biorefinery.