The contribution of atmospheric precipitation to volatile organic compound (VOC) removal from the atmosphere remains a matter of scientific debate. The aim of this study was to examine the potential of rainwater for benzene, toluene, ethylbenzene and xylene (BTEX) scavenging from ambient air. To that end, air and rainwater samples were collected simultaneously during several rain events that occurred over two distinct time periods in the summer and autumn of 2015. BTEX concentrations in the gaseous and aqueous phases were determined using proton transfer reaction mass spectrometry. The results reveal that the registered amounts of BTEX in rainwater samples were higher than those predicted by Henry's law. Additional analysis, including physico-chemical characterization and source apportionment, was performed and a possible mechanism underlying the BTEX adsorption to the aqueous phase was considered and discussed herein. Finally, regression multivariate methods (MVA) were successfully applied (with relative errors from 20%) to examine the functional dependency of BTEX enrichment factor on gaseous concentrations, physico-chemical properties of rainwater and meteorological parameters.