A method is proposed for the gas-chromatographic determination of glycols as bis(diethoxyphosphoryl)alkanes formed by the Atherton-Todd reaction with diethyl phosphite. Gas-chromatographic and mass-spectrometric characteristics of the derivatives obtained are studied. Conditions of the phosphorylation reaction are optimized. The method is applied to the determination of the residual amounts of glycols in oligomeric glycol-o-phthalates.