The calculations for a water‐acetonitrile‐substituted phenols system and the comparison with the experimental parameters will be given. Here we study change in the nature of the interactions into the system with donor and acceptor electron substituents on the phenolic ring, the structures, relative energies and harmonic frequencies. The conformers showed a significant difference in the OH and CN band shift depending on the type of the hydrogen bond formed and the position of the substituent on the phenolic ring. The cyclical hydrogen bonds between water‐acetonitrile and substituted phenol OH are important evidence of the relative stability in the system under study.