Knowing the temperature dependence of the organic carbon/water partition ratios (K OC ) of volatile methylsiloxanes (VMS) is required to understand their environmental fate. We measured the K OC of two linear VMS (lVMS), three cyclic VMS (cVMS), and six polychlorinated biphenyls (PCBs) at 25, 15, 10, and 5 °C and calculated their enthalpies and entropies of sorption to organic carbon (ΔH OC and ΔS OC , respectively). The ΔH OC of VMS ranged from −79.2 to −45.8 kJ mol −1 , while the ΔH OC of the PCBs ranged from −68.7 to −29.3 kJ mol −1 . Previously reported measurements of the enthalpy of phase change between octanol and water (ΔH OW ) for cVMS (11.3−68.8 kJ mol −1 ) differed substantially from our ΔH OC measurements, even showing different signs (negative versus positive). Literature data of ΔH OC and ΔH OW for PCBs (−61 to −17 kJ mol −1 ) are closer to our measured values of ΔH OC for the PCBs showing the same sign (negative) with differences within a factor of 2 in the majority of the cases. Comparison of all available data for PCBs and VMS indicated that there may be important differences between ΔH OC and ΔH OW , especially for the VMS. Therefore, assuming ΔH OC equals ΔH OW in environmental fate models may be a source of substantial error.