This study investigated the membrane fouling behaviors triggered by different characteristics of anaerobic digestion (AD) effluents in the operation of 851-h membrane distillation (MD). The AD effluents with different concentration factors (CF) were used as the feed separately. Results illustrated a stable normalized water flux in the treatment of raw AD effluent (CF = 1) over the 851-h MD experiment, showing negligible membrane fouling. While the sharp decreases in normalized water flux occurred when treating the concentrated AD effluents. The membrane fouling mechanism tended to change from inorganic scaling to organic fouling when the CF value increased from 1 to 3, while the combination of organic and inorganic fouling dominated the membrane fouling when CF was 5. Inorganic fouling was further intensified when the CF value increased to 10. The regression analysis demonstrated that the complete blocking model was the dominant development mechanism for CF = 3 treatment. The membrane fouling mechanism of CF = 5 treatment switched from the cake filtration model in the intermediate phase to the standard blocking model in the final phase. Additionally, there was a transition from the complete blocking model to the standard blocking model for CF = 10 treatment. The study may provide an in-depth knowledge of membrane fouling control during the actual AD effluent concentrating process.