Abstract The electrochemical properties of the triarylpyridinium salts were studied. The effect of functional substituents on redox properties has been investigated in detail. Electrochemical reduction of salts to the anion in acetonitrile is the result of two one‐electron‐transfer steps through the stage of the radical formation and its subsequent reduction (EE electrochemical mechanism). A correlation between the reduction potentials and the structure of the salts was established.