This work deals with the optimization of the concentration of volatile fatty acids (VFAs) using low-pressure reverse osmosis (LPRO) membranes. Membrane filtration of a synthetic solution simulating the product of biomass hydrolysis was performed. Experiments were run on two flat-sheet XLE membranes under 22 and 25 bar in continuous operation mode. Separation efficiency was evaluated for different recoveries. A correlation between the osmotic pressure of the concentrate and the parameter Rc, representative of the separation efficiency, was found. Under the conditions of the present study and taking into consideration the rejection properties of the applied membrane, a recovery of 33% and 44% is recommendable to maximize the ratio between the concentration of acetate in the concentrate and permeate and thus increase the total reclaim of acetic acid.