Effluents of anaerobic processes still contain valuable components, among which volatile fatty acids (VFAs) can be regarded and should be recovered and/or used further in applications such as microbial electrochemical technology to generate energy/energy carriers. To accomplish the separation of VFAs from waste liquors, various membrane-based solutions applying different transport mechanisms and traits are available, including pressure-driven nanofiltration (NF) and reverse osmosis (RO) which are capable to clarify, fractionate and concentrate salts and organics. Besides, emerging techniques using a membrane such as forward osmosis (FO) and supported liquid membrane (SILM) technology can be taken into consideration for VFA separation. In this work, we evaluate these four various downstream methods (NF, RO, FO and SILM) to determine the best one, comparatively, for enriching VFAs from pH-varied model solutions composed of acetic, butyric and propionic acids in different concentrations. The assessment of the separation experiments was supported by statistical examination to draw more solid conclusions. Accordingly, it turned out that all methods can separate VFAs from the model solution. The highest average retention was achieved by RO (84% at the applied transmembrane pressure of 6 bar), while NF provided the highest permeance (6.5 L/m2hbar) and a high selectivity between different VFAs.