Bioaccessibility extractions are increasingly applied to measure the fraction of pollutants in soil, sediment and biochar, which can be released under environmentally or physiologically relevant conditions. However, the bioaccessibility of hydrophobic organic chemicals (HOCs) can be markedly underestimated when the sink capacity of the extraction medium is insufficient. Here, a novel method called “Membrane Enhanced Bioaccessibility Extraction” (MEBE) applies a semipermeable membrane to physically separate an aqueous desorption medium that sets the desorption conditions from an organic medium that serves as acceptor phase and infinite sink. The specific MEBE method combines HOC (1) desorption into a 2-hydroxypropyl-β-cyclodextrin solution, (2) transfer through a low-density polyethylene (LDPE) membrane and (3) release into ethanol, serving as analytical acceptor phase. The surface to volume ratio within the LDPE membrane is maximized for rapid depletion of desorbed molecules, and the capacity ratio between the acceptor phase and the environmental sample is maximized to achieve infinite sink conditions. Several experiments were conducted for developing, optimizing and pre-testing the method, which was then applied to four soils polluted with polycyclic aromatic hydrocarbons. MEBE minimized sample preparation and yielded a solvent extract readily analyzable by HPLC. This study focused on the proof-of-principle testing of the MEBE concept, which now can be extended and applied to other samples and desorption media.