Abstract The novel synthesis of unsymmetrical 1,1’‐bibenzimidazoles is described. The key N−N bond was introduced on 1H ‐benzimidazole or 1H ‐benzimidazole‐2‐sulfonic acid by N‐amination with hydroxylamine‐ O ‐sulfonic acid (HASA). The precursors, 1‐[(2‐nitrophenyl)amino]‐ 1H ‐benzimidazoles, were prepared by nucleophilic aromatic substitution of 1‐fluoro‐2‐nitrobenzene with 1H ‐benzimidazole‐1‐amines. The synthesis was demonstrated on 11 novel 1,1’‐bibenzimidazoles, which were prepared in the final step by one‐pot reduction/cyclization with DMF or DMA acetals under mild acidic conditions in good overall yields.