The S(O,N)‐benzyl ethers of N‐arylquinone imines undergo cyclization under the action of bases to form products of the benzothiazol, benzoxazole, and benzimidazole series, while under thermal conditions they undergo a non‐catalyzed rearrangement to form spiro‐cyclohexadiene derivatives of benzazines. The benzimidazole, spirobenzothiazine, and spirobenzoxazine structures were supported by the x‐ray diffraction method. The possibility of intramolecular photochemical cyclization was investigated; ortho‐S(O,N)‐benzyl‐substituted N‐arylquinone imines show high photostability under UV irradiation. The features of the cyclization processes of quinone imine derivatives were revealed by DFT calculations using the wB97XD/6‐311++G** method.