Herein, the efficient role of ultrasonic irradiation both in synthesis of Zr based porous coordination polymer (Zr-PCP) nanoparticles and boosting its catalytic activity, towards the benzimidazoles synthesis is represented. We use an amine based ligand (amino-terephthalate) for PCP and we exhibit that it can have a synergistic catalytic activity. In this work, a unique nano-engineering of cooperative and synergistic catalytic activity of zirconium, as a Lewis acid, and aminophenylene, as an organocatalyst, in the synthesis of heterocycles is presented for the synthesis of benzimidazole from cascade reaction of phenylene diamine with aldehyde at ambient temperature. Zr and amine groups of the Zr-PCP are active catalytic sites which in combination with the ultrasonic irradiation leads to a high selectivity and rapid catalytic production of benzylimidazoles. N2 adsorption-desorption along with BJH analyses confirm the microporosity of the catalyst and recyclability shows that the catalyst is green and sustainable heterogeneous microporous catalyst.