Pretreatment combining FeCl3 and Tween80 was performed for cellulose-to-ethanol conversion of eucalyptus alkaline peroxide mechanical pulping waste fibers (EAWFs). The FeCl3 pretreatment alone showed a good effect on the enzymatic hydrolysis of EAWFs, but inhibited enzyme activity to some extent. A surfactant, Tween80, added during FeCl3 pretreatment was shown to significantly enhance enzyme reaction by eluting enzymatic inhibitors such as iron(III) that are present at the surface of the pretreated biomass. Treatment temperature, liquid-solid ratio, treatment time, FeCl3 concentration, and Tween80 dosage for pretreatment were optimized as follows: 180 °C, 8:1, 30 min, 0.15 mol/L, and 1% (w/v). Pretreated EAWFs under such optimal conditions provided enzymatic glucose (based on 100 g of oven-dried feedstock) and substrate enzymatic digestibility of EAWFs of 34.8 g and 91.3% after 72 h of enzymatic hydrolysis, respectively, with an initial cellulase loading of 20 FPU/g substrate.