To investigate the treatment performance of membrane-coupled anaerobic volatile fatty acids fermentor system, the effects of operational parameters for volatile fatty acids production were evaluated through experiments and a mathematical model. The volatile fatty acids recovery ratio was largely affected by the change of hydraulic retention time, reaching its maximum value at 12 hrs. Over the range of hydraulic retention time 8 to 96 hrs, the volatile fatty acids recovery ratio decreased with the increase of hydraulic retention time above 12 hrs, while the ratio of mineralization and gasification increased. Hydraulic retention time and membrane filtration ratio should be maintained less than 1 day and above 0.9, respectively, to attain over 40% of organic materials recovery ratio at 10 days of solids retention time. When the hydrolysis rate constant was 0.01 hr-1, the organic loading rate should be maintained at above 1.0 (kgC/m3/day) to attain over 45% of volatile fatty acids recovery ratio. Based on experimental and simulated results, membrane-coupled anaerobic volatile fatty acids fermentor system was thought to be effective for dissolved organics recovery from coagulated sewage sludge.