Since the membrane distillation (MD) has attached to anaerobic fermentation (AF) process, all suspended solid contents including acetogenic and methanogenic microorganism can be retained inside the system to expect the more effective degradation of organic matter under operational parameters of hydraulic retention time (HRT) and solid retention time (SRT). In this study, we only focused to monitor the carbohydrate and protein parameters inside the single AF compared to the AF coupled with MD. Synthetic high-strength wastewater was used as a substrate by using the composition of 99 g glucose/L, 34 g/l NH4HCO3, 60 g yeast extract/L, 3 g KH2PO4/L, and K2HPO4 g K2HPO4/L. HRT was 20 days with feed flowrate of 0.3 L/d. The steady state of single AF and the AF coupled with MD were monitored for 60 days and 30 days, respectively. The configuration of AF coupled with MD used the circulation rate of 1.5 L/min, cross flow velocity of 0.014 m/s, and temperature difference of 30℃. pH changed from 7.6 in the single AF to 8.2 in the AF coupled with MD. The wastewater quality was analyzed everyday according to total carbohydrate, soluble carbohydrate, total protein, and soluble protein in the influent and effluent of both reactors. The average removal of total and soluble carbohydrate in the single AF were 98.4% and 97%, respectively. The average removal of total carbohydrate in the AF coupled with MD was 98% (in the effluent AF) and the average rejection was 97.8% (in the effluent MD as permeate). The average removal of soluble carbohydrate in the AF coupled with MD was 95% (in the effluent AF) and the average rejection was 97.5% (in the effluent MD as permeate). For the single AF, the average increased of total protein was 86% while the average removal of soluble protein was 42%. The average total protein in the AF coupled with MD increased to 75.6% in AF and the average rejection was 99.7% in the effluent MD. Furthermore, the average soluble protein in the AF coupled with MD increased to 87.7% in AF and the average rejection was 97% in the effluent MD. After attaching MD to AF, the hydrolysis microbial biomass changed by reducing the concentration of total protein and increasing the concentration of soluble protein in the AF process. This effect warrants further investigation which associated with changes in the microbiology in the microbiology or physicochemical aspects.