AbstractMolecular ionization potentials for series of compounds of the type XC6H4CN, XC6H4CH2CN and XC6H4N(CH3)2 have been measured using the retarding potential difference technique (RPD. technique). The effect of the various substituents X is better correlated through the electrophilic Brown σp+ constants than through Hammett's σp values. No meta‐para orientation effect is observed. For all the disubstituted phenyl compounds studied, the effect of the second substituent is affected by the electron‐releasing power of the original substituent. Ionization potentials calculated by using the semi‐empirical method of equivalent orbitals are in good agreement with the experimental values.