Abstract A study was carried out on the electrophilic substitution reactions such as chloromethylation, bromination, sulfonation, nitration, and acylation of 2-(3′-furyl)-1-methyl- 1H-benzimidazole in acid media. All these reactions proceed at C (2) and C (5) of the furan ring. Quantum-chemical calculations of the three-dimensional structure of such heterocyclic systems are given.