Passive sampling is a very attractive alternative to active sampling due to its simplicity and low cost. Among the passive samplers used in air analysis, permeation passive samplers are the least affected by ambient conditions, including humidity, air currents, and temperature changes. The biggest drawback of permeation passive samplers is the need to calibrate them experimentally for each individual target analyte. The paper presents the results of research on the calibration of permeation passive samplers based on physicochemical properties of the analytes. Strong correlations were found between the calibration constants of the samplers and the number of carbon atoms among families of compounds (R2 ranging from 0.8507 for alcohols to 0.9995 for aromatic hydrocarbons), the molecular weights of the compounds (R2 = 0.8742), their boiling points (R2 = 0.8911), and linear temperature-programmed retention indexes (R2 = 0.9225). The last correlation makes it possible to estimate the calibration constants for unidentified analytes, which is impossible when the conventional procedure is used. This makes it possible to deploy permeation passive samplers in the same way in which active sampling is deployed.