A simple and novel scheme for preparing hierarchical porous 4A-zeolite was introduced in this study. By Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), X-Ray Powder Diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Simultaneous Thermal Analysis (STA), Transmission Electron Microscopy (TEM), CO2 adsorption–desorption (BET and BJH) and UV–vis spectra, the silver nanoparticles supported samples of microporous-macroporous hierarchical 4A-zeolite (Ag/P-4A-zeolite) were proven to be successfully synthesized. TEM and CO2 adsorption–desorption images indicated the presence of microporous and the formation of macroporous. XRD, ICP-AES and UV–vis spectra indicated that obtained P-4A-zeolite possess silver nanoparticles. In addition, the catalytic results showed that the silver loaded hierarchical porous 4A-zeolite (Ag/P-4A-zeolite) composite catalyst had catalytic performance in hydrogenation of 4-nitrophenol (4-NP) and epoxidation of styrene.