Short-chain chlorinated paraffins (SCCPs) are under regulation through the European Water Framework Directive and were recently classified as POPs. Consecutively, the increasing use of middle-chain chlorinated paraffins (MCCPs) becomes of growing concern. Knowledge on the occurrence of chlorinated paraffins (CPs) is still scarce particularly in water phase. To achieve sufficient method sensitivity, the passive sampling approach, acting as a relevant alternative to usual grab sampling, has been considered only very recently for the monitoring of CPs in water. The present work aimed at determining the diffusion coefficients in silicone (D s) and the silicone-water partition coefficients (K sw) of various CP groups, having different chlorine contents and carbon chain lengths, in four commercial CP mixtures. Log D s (-10.78 to-10.21) was found to vary little and to be high for the groups of CPs studied. Thus, their uptake in silicone is controlled by the water boundary layer, which allows to consider the release of performance and reference compounds for infield estimation of the sampling rate. Moreover, CPs partitioned strongly towards silicone rubbers. Both the chlorination degree and the carbon chain length of CPs cause large uncertainties in the partitioning between silicone and water (log K sw between 4.85 and 6.30), indicating that instead of an average value, differentiated K sw should be used to estimate aqueous CPs more accurately. Even so, the probable influence of chlorine atoms position on polarity and partitioning may be an argument for favoring sampling in the kinetic stage.