This study compared the evaporation and skin absorption profiles of four fragrance chemicals in in vitro skin penetration studies performed in conditions of airflows of low velocity with and without trapping of the evaporated volatiles. The presence of a trapping chamber above the skin surface slowed down the evaporation of the chemicals, possibly due to formation of a gaseous stagnant layer of greater thickness than the one existing at the skin surface in the real-life conditions of multidirectional and/or turbulent flows. In addition, the use of a trapping chamber considerably influenced the distribution of the fragrance chemicals in the skin layers and resulted in 2- to 8-fold increase of the doses available for systemic absorption. Such unrealistic overestimation of the percutaneous absorption can significantly impact the risk assessment of topically applied volatile chemicals and can lead to defining unrealistic margins of safety.