Most of the conventional treatments of waste-activated sludge (WAS) are devoted to their minimization and destruction. On the other hand, the biomass contained in WAS can be utilized as a valuable source of renewable carbon. In this study, the influence of different pretreatments (ultrasonication, chemical, thermal, and combined pretreatments) was explored for sludge solubilization. Effects of the pretreatments were investigated as a function of the solubilization of total solids (TS), volatile solids (VS), and chemical oxygen demand (COD). Concentrations of soluble carbohydrates and total nitrogen were also measured. The most effective pretreatment to hydrolyze sludge was found to be the combined alkali−thermal (pH 12, 75 °C) pretreatment method, leading to TS and vs. solubilization of 9.6% and 17.2%, respectively. Soluble COD, carbohydrates, total nitrogen, and proteins estimated in the liquid phase were 5235 mg/L, 732 mg/L, 430 mg/L, and 2688 mg/L, respectively. Thus, the alkali−thermal method could be used for efficient valorization of WAS. Moreover, the solid fraction from all pretreated samples was further subjected to thermogravimetric analysis to estimate its potential for bioenergy from its higher heating value (HHV), which was found to be in the range of 10−11.82 MJ/kg. This study can provide better insight into the efficient valorization of liquid and solid phases of sludge after pretreatment.