Cloud droplets are able to trap many gaseous compounds and represent a very reactive media in the atmosphere. However, phase-partitioning of Volatile Organic Compounds (VOCs) between gaseous phase (interstitial air) and atmospheric liquid phase (cloud droplets) is still poorly characterized. In the present work, air samples and cloud water were collected simultaneously and hydrophobic organic compounds from anthropogenic and biogenic origins were quantified in order to evaluate their air/water partitioning. For this, cloud events were sampled at the puy de Dôme station (PUY). A new analytical approach was optimized to explore dissolved VOCs in the aqueous phase by Stir Bar Sorptive Extraction (SBSE) and gaseous samples were collected using sorbent tubes. All samples were analyzed by Thermal Desorption (TD) Gas Chromatography (GC) coupled with Mass Spectrometry (MS). Extraction efficiencies by SBSE vary between 22% and 97% and the detection limit of VOCs in aqueous cloud samples lies between 1.0 and 8.7 ng L−1. Experimental partitioning is evaluated towards the theoretical one described by the Henry's Law constants. Our results show that observed concentrations of hydrophobic VOCs are supersaturated by a factor of 10–103 in comparison with Henry's law equilibrium. Calculations have been performed to evaluate the potential role of adsorption at the air/water interface and of sorption with non-dissolved organic carbon. However, the supersaturation in the cloud droplets requires more laboratory experiments to understand processes at the air/water interface and constrain cloud chemistry models.