Reducing the pretreatment cost of lignocellulosic biomass by utilizing alkali to alter its recalcitrant nature is an effective method for biofuel production. In this experiment, 1.5% KOH solution and its black liquor (spent liquor of KOH) (BL) were applied to pretreat corn stover (CS) at a temperature of 20 °C to enhance the digestibility for anaerobic digestion (AD). Results showed no significant difference in weighted average methane content on the basis of experimental methane and biogas yields between BL-treated and original KOH-treated CS after AD. The BL process significantly increased the overall methane yield by 52.4% compared with untreated CS (135.2 mL/gVS), whereas no significant difference between the overall methane yields of 1.5% KOH-treated and BL-treated CS was observed. In addition, the BL process significantly saved water and KOH consumption, by 56.2% and 57.4%, respectively, compared with the 1.5% KOH pretreatment. Overall methane production was well explained by the modified Gompertz model. The physiochemical changes to CS after BL pretreatment were confirmed by SEM, FTIR, and XRD analyses. Our findings collectively suggest that recycling and reuse of KOH black liquor might be an efficient method for lignocellulosic biomass treatment and have the capability to reduce input costs in future AD processes.