A systematic study has been undertaken of the chromatographic characteristics of a certain number of β-cyanoethyl derivatives of polyols, thiols, phenols, and thiophenols. The parameters measured for each phase were: limiting temperature for use, polarity P, and retention index of benzene. The tetracyanoethyl derivative of pentaerythritol and, above all, the dicyanoethyl derivatives of the three isomeric diphenols possess good temperature stability and show high polarity. It was possible to confirm that the retention index of benzene generally increases in the same way as the polarity. Finally, some relationships could be established between the chemical structure of the phase and its retentivity for benzene, or its polarity.