Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are a group of important persistent organic pollutants. In the present study, the three-dimensional holographic vector of atomic interaction field (3D-HoVAIF) method is used to describe the chemical structures of PCDD/Fs. After variable screening using a stepwise multiple regression (SMR) technique, the linear relationships among six physicochemical properties of PCDD/Fs and 3D-HoVAIF descriptors are built using a partial least-squares (PLS) regression model. The results show that the 3D-HoVAIF descriptors can be used to express the quantitative structure-property relationships of PCDD/Fs. The predictive capabilities of the models have also been confirmed by leave-one-out cross-validation. The optimum model has been used to estimate values for PCDD/Fs for which no experimental data on physicochemical properties are available. Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Environmental Science and Health: Part A to view the free supplemental file.