This paper was designed and prepared a new nanoarchitectonics of LDH/polymer composite with specific morphology. For this purpose, CTAB surfactant was used to control the morphology of layered double hydroxide (LDH) and to prepare LDH/polymer nanocomposites (LDH–APS–PEI–DTPA). The polymer was synthesized using diethylenetriaminepentaacetic acid (DTPA), polyethylenimine and used with LDH to form a nanocomposite with high thermal stability. Subsequently, the prepared nanocomposite was identified using FTIR, EDX, TGA, XRD, FESEM, and BET techniques. In addition, the prepared LDH–APS–PEI–DTPA nanocomposite was used as a heterogeneous and recyclable catalyst for the synthesis of imidazole derivatives under green conditions. The results showed that the LDH–APS–PEI–DTPA nanocomposite benefit from suitable morphology, simple preparation, high catalytic activity, and high surface area. Also, the proposed LDH–APS–PEI–DTPA heterogeneous catalyst showed high stability and reusability for five consecutive runs which was consistent with the principles of green chemistry.