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In this study, the gas-phase retention volume behavior of four highly volatile organophosphate esters (OPEs) on polyurethane foam (PUF) was studied using a frontal chromatogram. The breakthrough volumes (V B) of trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPrP), and tri-n-butyl phosphate (TnBP) were 0.33, 0.59, 10.5, and 32.4 m3, respectively. A significant negative correlation was found between the logarithm value of V B and the subcooled liquid vapor pressure (P L) with an r 2 of 0.905, indicating that the vapor penetration depends on both the volatility and total air volume. The enthalpy of desorption and vaporization (Δ H S −Δ H V) showed a significant difference between the tested OPEs and polycyclic aromatic hydrocarbons (PAHs), revealing that the strength of the sorption interaction of the tested OPEs vapor on PUF should be different from that of PAHs. The PUF-air partition coefficients (K PUF-air) of the tested OPEs ranged from 4.3 to 8.1, which were lower than those of three-to four-ring PAHs (7.02–10.2) and organochlorines (8.01–9.72), revealing that the partition of highly volatile OPEs on PUF is lower than that of low-volatile compounds. The PUF/XAD cartridge improved the absorption efficiency of the tested OPEs; however, its sorptive capacity was still limited. [Display omitted] • The breakthrough volumes of four high volatile OPEs on PUF column were determined by frontal chromatograms. • The breakthrough volumes of the tested OPEs are much lower than three to four ring PAHs. • There are significant differences in the sorption interaction on PUF between the tested OPEs and low volatile compounds. • XAD resins can improve the sorptive capacity for high volatile OPEs. [ABSTRACT FROM AUTHOR]