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Solvent activities of seven organic solvents in mixtures with PDMS (Polydimethylsiloxane) of different molecular weights have been measured at 298.15 and 313.15 K using the vapor sorption technique. The results have been used for testing the thermodynamic consistency of an extended version of Flory's theory. In this theoretical approach a more detailed expression of the combinatorial entropy is used and found to be superior to the common Flory‐Huggins expression.