We present an efficient method for the synthesis of 1,2,3-triazol-4-linked benzo[d]imidazo[1,2-a]imidazol-3-amine derivatives via sequential Groebke–Blackburn–Bienaymé/click reaction. This two-step, one-pot synthesis was started with Groebke–Blackburn–Bienaymé reaction between 4-(prop-2-yn-1-yloxy)benzaldehyde, 2-aminobenzimidazole, and isocyanides under solvent-free conditions. The resultant Groebke–Blackburn–Bienaymé adduct underwent a click reaction with (azidomethyl)benzenes in a tert-buthanol/water mixture as solvent at room temperature in the presence of Et3N and sodium ascorbate to produce the desired products in good yields.