2,6-Bis(5-amino-1H-benzimidazol-2-yl)pyridine was prepared and characterized by FT-IR, elemental analysis, H-1 NMR, and C-13 NMR spectroscopic methods. Then, some new poly(benzimidazole-amide)s (PBA)s were synthesized by polymerization of the corresponding diamine and different diacids. The structures of synthesized polymers were characterized by FT-IR, H-1 NMR, elemental analysis, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and field-emission scanning electron microscopy (FE-SEM). The obtained PBAs exhibited good yields and high thermal stability and were soluble in polar aprotic organic solvent. Due to the existence of benzimidazole moieties in polymer's structure, it was expected that the synthetic polymers would tend to form complexes with metal ions. So, a new PBA/Ni nanocomposite was prepared and characterized by FT-IR, TGA, XRD, FE-SEM, energy dispersive X-ray spectroscopy, and transmission electron microscopy. Morphological studies revealed that the metal nanoparticles were dispersed in the polymer matrix without any aggregation. PBA/Ni nanocomposite was used as a catalyst in the reduction of styrene with hydrazine.