The management of secondary sludge from aerobic treatment of effluents from the cellulose industry is a current problem. The usual ways of disposal do not provide added value to the waste as they assume an economy based on “take-make-waste” (linear economy). In this work, thermal hydrolysis (TH) and anaerobic digestion (AD) are proposed to valorize this biosludge. Based on a Doehlert experimental plan, a response surface methodology (RSM) defined by seven different TH conditions is proposed. After TH, biomethanation potential (BMP) tests were performed to evaluate the AD possibilities. The TH conditions cover a temperature range between 125 °C and 205 °C and a reaction time from 15 min to 45 min. The TH process was successful in enhancing the bioavailability of the waste, increasing the concentration of soluble organic matter quantified by chemical oxygen demand of the soluble fraction (CODs), and decreasing the concentration of volatile suspended solids (VSS). However, response surfaces performed for CODs and VSS revealed the existence of optimums, which demonstrated the adverse effects of the more severe TH conditions. Organic matter solubilization was confirmed by microscopic observations. The amount of suspended organic matter after TH is reduced by two to three times compared to the untreated value. The subsequent BMP of the hydrolyzed waste increases between 100% and 220% compared to the untreated condition, wich had a BMP value of 84 NmL CH4 gVS−1. The response surface determined for the BMP reveals the presence of a maximum point of methane production at 202 °C for 31 min, which differs from the maximum CODs value observed at 196 °C for 40 min.