A novel functional bio-nanocomposite was prepared by deposition of Ag nanoparticles onto the surface of natural eggshell membrane fibers. Practically, the functional groups exposed on the fiber surface can provide locations to anchor Ag ions when immersed into metal precursor solution. The synthesized small-sized Ag nanoparticles with uniform distribution is well decorated on the surface of interwoven fibers of eggshell membrane. The effectiveness of the as-prepared AgNPs/ESM composites as a solid phase heterogeneous catalyst has been evaluated, for the first time, on the well-known 4-nitrophenol reduction to 4-aminophenol in the presence of excess borohydride. Moreover, the kinetics of the reduction reaction was investigated at different temperatures to determine the activation energy. This work provides an important example in the introduction of natural membranes for the fabrication of functional hybrid nanocomposites which could be very useful in varying fields.