[reaction: see text] A novel intramolecular SNAr rearrangement observed during the S-alkylation of benzoimidazole-2-thione with alpha-haloacetophenone is reported. The rearrangement led to the formation of a new benzoimidazole-based intermediate, which is further utilized for the generation of a new biheterocyclic indole-benzimidazole derivatives with a two-point diversity.