The presence of surfactants in waste activated sludge (WAS) system is generally regarded as beneficial to sludge treatment such as enhancing sludge dewatering and improving value-added fermentation products generation. However, in this study, it was firstly found that sodium dodecylbenzene sulfonate (SDBS, a typical surfactant) obviously increased toxic hydrogen sulfide (H2S) gas production from WAS anaerobic fermentation at environmentally relevant concentrations. Experimental results showed that H2S production from WAS significantly increased from 53.24 × 10−3 to 111.25 × 10−3 mg/g volatile suspended solids (VSS) when SDBS level increased from 0 to 30 mg/g total suspended solid (TSS). It was found that SDBS presence destroyed WAS structure and enhanced sulfur containing organics release. SDBS reduced the proportion of α-helix structure, damaged disulfide bridges and protein conformation, and effectively destroyed protein structure. SDBS promoted sulfur containing organics degradation and provided more readily hydrolyzed micro-molecule organics for sulfide production. Microbial analysis showed that SDBS addition enhanced the abundance of functional genes encoding protease, ATP-binding cassette transporters, and amino acids lyase, enhanced the activities and abundance of hydrolytic microbes, thus increased sulfide production from the hydrolysis of sulfur containing organics. Compared with the control, 30 mg/g TSS SDBS increased organic sulfurs hydrolysis and amino acids degradation by 47.1 % and 63.5 %, respectively. Key genes analysis further showed that SDBS addition promoted sulfate transport system and dissimilatory sulfate reduction. SDBS presence also lowered fermentation pH, promoted the chemical equilibrium transformation of sulfide, thus increased H2S gas release.