Two methods of determining the complexation constants of “volatile organic compound (VOC) – 2-hydroxypropyl-β-cyclodextrin (HP-β-CD)” were tested by headspace gas chromatographic analysis. It was shown that the complexation constants of VOC with HP-β-CD calculated using 2 approaches were comparable with each other. The increase in complexation constants was observed for homologues with the increase in the molar mass and dipole moment of molecules.