To determine the potential for improving biomass enzymolysis, a combined oxidization and liquid ammonia pretreatment (OD-LAT) was employed for bamboo. The effects of oxidant, bamboo ages, and species on the pretreatment effectiveness and subsequent enzymolysis were studied. Under the optimal OD-LAT pretreatment and enzymolysis of the B-NA bamboo Neosinocalamus affinis, the glucan and xylan conversion reached 83.85% and 78.66%, respectively, and approximately 59.7-68.5 g of fermentable sugars can be produced per 100 g of dry bamboo, which was an approximately 5-8 fold increase compared with untreated sample. The H2O2 loading of 1.0 was the optimal oxidant dosage for the OD-LAT process. The OD-LAT pretreatment was only suitable for bamboo under three-year-old, and it significantly improved the enzymolysis of B-NA and B-BM, while it was limited to B-DO and B-PP. The pretreatment effects of bamboo were not only related to composition but also to the bamboo age, species, macro-structures and micro-structures.