Potassium ferrate has strong oxidation in both acid and alkali environments, which has attracted extensive attention. However, the impact of the pH environment on this coupling process with the goal of resource recovery has not received attention. Under the goal of the efficient recovery of organic acid, the changes of solid–liquid characteristics of sludge after acid and alkaline ferrate pretreatment and during anaerobic digestion were discussed. The results showed that compared with blank control groups, after alkaline ferrate pretreatment, the volatile suspended solids (VSSs) decreased the most, reaching 28.19%. After being pretreated with alkaline ferrate, the sludge showed the maximum VFA accumulation (408.21 COD/g VSS) on the third day of digestion, which was 1.34 times higher than that of the acid ferrate pretreatment. Especially in an alkaline environment, there is no need to add additional alkaline substances to adjust the pH value, and the effect of sludge reduction and acid production is the best.