This study compared enzymatic saccharification of sugarcane bagasse (SCB) after application of two different pretreatment methods, Fenton pretreatment (FP) and BiFeO Fenton-like pretreatment (BFP). The composition, morphology and structural properties of SCB with different pretreatments were analyzed. Results showed that, after BFP, the yield of reducing sugar of SCB under enzymatic saccharification for 72 h was 25.8%, and the sugar conversion rate was 36.6%, which were 2.2 and 2.4-fold those of the FP, respectively. Moreover, the removal of hemicellulose and delignification in the BFP was more severe than that in the FP. The determination of hydroxyl radical (OH) in the two different Fenton processes revealed that the OH generated in the BiFeO Fenton-like system was higher in concentration and longer in action time than that in the Fenton system, which was likely key to the stronger effect of BFP than FP on the enzymatic saccharification of SCB.