Methods of preparation of 2-trihalogenomethyl-benzimidazoles, -benzothiazoles, and -benzoxazoles have been investigated. It has been shown that the reaction of the mono-salts of o-phenylenediamines, o-aminophenols, and o-aminothiophenols with trichloroacetonitrile or trichloroacetimidate esters affords 2-trichloromethyl substituted benzimidazoles, benzoxazoles, and benzothiazoles. This method has been extended to the preparation of 2-trichloromethyl-2-azolines. A general method of preparation of 2,2′-bibenzimidazolyls is also described.