In this work we analyzed the strength of the intermolecular forces between biodiesel and the entrainer and their influence on the entrainer's ability to interact with biodiesel. Furthermore we investigated the influence of the chemical structure of an entrainer to the interaction with biodiesel. For this purpose the activity coefficients γ at infinite dilution of acids, aldehydes, ketones and alcohols in biodiesel were measured with the method of headspace gas chromatography (HSGC). Short-chained acids showed the highest interaction of the analyzed entrainers caused by their ability to build hydrogen bonds with biodiesel. Increased chain length of the acids cause reduced interaction with biodiesel, which is mainly due to the higher obstruction of the acid molecule and therefore the reduced ability to build hydrogen bonds with biodiesel. Aldehydes, ketones and alcohols showed lower interaction with biodiesel compared to the acids. Longer-chained alcohols showed increased interaction with biodiesel due to the raised London Forces and an inductive +I effect of the molecule chain.