An efficient solution-phase parallel synthesis of multisubstituted 5-aminobenzimidazoles is described. The two fluorine atoms of 1,5-difluoro-2,4-dinitrobenzene (DFDNB) are sequentially and quantitatively replaced by nucleophiles. Simultaneous reduction of aromatic m-dinitro groups by Pd-C/HCOONH(4) results in 2,4,5-benzenetriamines, which are continuously condensed with aldehydes to successfully construct the benzimidazole ring without additional oxidants. The free aromatic amino group is further modified by anhydrides, isocyanates, isothiocyanates, and sulfonyl chlorides. All the reactions involved here are highly effective in giving the desired products at room temperature. Four diversity points are introduced in the final products.