Higher economic returns and carbon–neutral benefits drive research shifting to volatile fatty acids (VFAs) recovery from sludge treatment. The novel natural deep eutectic solvents (NADES) based pretreatments of waste activated sludge (WAS) were proposed, focusing on sludge dewaterability, organics dissolution, and subsequent production of VFAs via anaerobic fermentation. Three different pretreatment methods, i.e., NADES treatment alone, NADES with 80 °C thermal treatment, and NADES with 180 °C hydrothermal treatment were systematically compared. The dewaterability of sludge significantly improved only when NADES assisted by thermal treatments, which was interpreted by a substantial decline in capillary suction time (CST) and water-holding capacity. All three pretreatments boosted the VFAs production from sludge (1.40–2.33 times compared with control), and increased the proportion of acetic acid by about 10 %. Results showed that the highest VFAs yield of 2728.71 mg COD/L was obtained from NADES combined with 180 °C hydrothermal treatment, which was increased by 133 % compared to the control. Such performance is much higher than a surfactant assisted hydrothermal treatment recently reported in the literature (increased by 27 %). Mechanistic studies elucidated that NADES stimulated sludge solubilization, enhancing the release of organic substrates for VFAs production. Further metagenomic analysis demonstrated that the hydrolytic-acidogenic bacteria were enriched after NADES treatments. Moreover, glycosyl transferases (GTs) and carbohydrate esterases (CEs) were the primary carbohydrate-active enzymes (CAZymes) enhanced by NADES addition. This study provides new insights into green solvents simultaneously enhanced sludge dewatering and resource recovery.