The main component of surfactant is linear alkylbenzene sulfonate (LAS), which is toxic to the ecological environment and can cause serious harm. In this study, some activated sludge was taken from the aerobic and anaerobic tank of a sewage treatment plant in Shenzhen, then cultivated and domesticated in a membrane bioreactor with artificial surfactant wastewater. The start-up phase of the reactor adapted the constant-flux filtration, and the HRT was 12 h. The pH was below 5.5, which needed the addition of NaHCO3 after 6 days to adjust to the more optimal level (pH 6.5–7.5). After operation for 20 days, the start-up of the system was considered successful. At the early stage, the removal rates of chemical oxygen demand (COD) and LAS were relatively stable, reaching as high as 85.49%–93.31% and 80%, respectively. When the LAS concentration reached over 175 mg/L and the COD declined to about 83%, the removal rate of LAS also significantly decreased. LAS removal rate further decreased to about 60% when the dosage reached 200 mg/L, indicating that the resistance of microorganisms against LAS toxicity was also limited. LAS degradation could have been mainly driven by Dechloromonas, Gemmata, Pseudomonas and Zoogloea in the system.