The paper presents the results of research on the calibration of permeation passive samplers equipped with polydimethylsiloxane (PDMS) membranes using the physico-chemical properties of the analytes. Strong correlations were found between the calibration constants of the samplers and the linear temperature-programmed retention indices of the analytes determined on columns coated with pure PDMS (r2 = 0.914). These correlations make it possible to estimate the calibration constants for unidentified analytes, which is impossible when using conventional procedures. This, in turn, enables the deployment of permeation passive samplers in the same way in which active samplers are deployed. The reproducibility of the calibration constants determined in different laboratories and retention indices determined using different chromatographic systems was very good, indicating that the calibration constants estimated using this approach should be reproducible as well. The approach proposed should lead to more widespread use of permeation passive samplers.