A facile, simple, and eco-friendly method using 4-acetamido-2,2,6,6-tetramethypiperidine-1-oxyl radical-oxidized curdlan (Oc) as both reducing and stabilizing agents was developed for the fabrication of silver nanoparticles (AgNPs) from silver nitrate (AgNO₃). The structure, morphology, and particle size of the as-prepared AgNPs were investigated by ultraviolet-visible spectroscopy, transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, and dynamic laser light scattering. The well-dispersed AgNPs were sphere like with a mean diameter of 15 nm. Their formation was dependent on reaction duration, reaction temperature, Oc concentration, and AgNO₃ concentration. Fourier transform-infrared and Raman spectra demonstrated that the as-prepared AgNPs can readily bind covalently with the carboxylate groups of Oc through the strong monodentate interaction in the reaction medium.