AbstractFree nitrous acid (FNA) serving as a pretreatment is an effective approach to accelerate sludge disintegration. Also, sodium dodecylbenzene sulfonate (SDBS), a type of surfactants, has been determined at significant levels in sewage sludge, which thereby affects the characteristics of sludge. Both FNA pretreatment and sludge SDBS levels can affect short-chain fatty acid (SCFA) generation from sludge anaerobic fermentation. To date, however, the combined effect of FNA pretreatment and SDBS presence on SCFA production as well as the corresponding mechanisms have never been documented. This work therefore aims to provide such support. Experimental results showed that the combination of FNA and SDBS treatment not only improved SCFA accumulation but also shortened the fermentation time. The maximal SCFA accumulation of 334.5 mg chemical oxygen demand (COD)/g volatile suspended solids (VSS) was achieved at 1.54 mg FNA/L treatment and 0.02 g/g dry sludge, which was respectively 1.79-fold and 1.41-fold of that from FNA treatment and sludge containing SDBS alone. Mechanism investigations revealed that the combined FNA pretreatment and SDBS accelerated solubilization, hydrolysis, and acidification steps but inhibited the methanogenesis. All those observations were in agreement with SCFA enhancement.