As the by-product in the biological sewage treatment, waste-activated sludge (WAS) always suffers from the difficulty of disposal. Anaerobic fermentation to achieve valuable carbon sources is a feasible way for resource utilization of WAS, whereas the process is always restricted by its biochemical efficiency. Hence, the WAS was used as the feedstock in this study. Alumina slag-modified biochar (Al@BioC) respectively from pine wood (PW) or fresh vinegar residue (FVR) was employed to stimulate the process of short-chain fatty acids (SCFAs) production during the anaerobic treatment of WAS. The results indicate that the addition of Al@BioC could facilitate the distinct increase in SCFAs yield (42.66 g/L) by 14.09% and acetate yield (33.30 g/L) by 18.77%, respectively, when compared with that in regular fermentation without Al@BioC addition. Furthermore, protein degradation was also improved. With the Al@BioCPW added, the maximum concentration of soluble protein reached 867.68 mg/L and was 24.39% higher than the initial level, while the enhancement in the group with Al@BioCFVR and without biochar addition was 12.49% and 7.44%, respectively. According to the results of 16S rDNA sequencing, the relative abundance of acid-producing bacteria (Bacteroidota and Firmicutes) was enriched, enhancing the pathways of protein metabolisms and the ability to resist the harsh environment, respectively. Moreover, Proteiniphilum under Bacteroidota and Fastidiosipila under Firmicutes were the main microorganisms to metabolize protein. The above results might provide a novel material for harvesting the SCFAs production, which is conducive to harmless disposal and carbon resource recovery.