Recovery of short-chain fatty acids (SCFAs) from waste activated sludge (WAS) by anaerobic fermentation (AF) is limited by the slow rate of WAS hydrolysis. Here, choline chloride (ChCl)-assisted thermal hydrolysis pretreatment (THP) was proposed to improve the hydrolysis rate and SCFA recovery from WAS. ChCl-assisted THP (140 °C, 30 min, 0.60 g/g TSS) increased the SCFA yield by 139 % compared to the control (unpretreated) group, rising from 2629 ± 190 mg COD/L to 6276 ± 153 mg COD/L, and raised the percentage of acetic acid from 28.7 % to 58.0 %. The hydrogen-bonding effect of ChCl facilitates sludge destruction by THP and induces oxidative stress through quaternary ammonium groups to destroy cells, thus creating a synergistic effect on WAS hydrolysis. In addition, ChCl-assisted THP promotes the production of SCFAs by increasing the activity of key enzymes and enriching hydrolyzing and acidifying bacteria. This article provides a new approach to enhance SCFA recovery from WAS.