This paper reports on the fabrication of material comprised of chitosan stabilized silver nanoparticles on the carbon paste and its electro-catalytic reduction toward 4-nitroaniline. The synthesized material was obtained when AgNO3 was mixed with chitosan as a stabilizing agent and NaBH4 as a reducing agent. The developed Chitosan-AgNPs has been confirmed using UV-Vis spectroscopy, X-Ray diffraction analysis, scanning electron microscopy (SEM) and infrared spectroscopy. The synthesized chitosan-Ag NPs exhibit particle size around 51 nm. To build a voltammetric sensor (Chitosan-Ag NPs/CPE), a carbon paste electrode has immersed in the liquid suspension of chitosan-Ag NPs, thus, it could be employed for electro-catalytic reduction of 4-NA in 0.1 M Britton-Robinson buffer solution (B-R, pH 2). Therefore, the reduction over-potential of 4-NA shifted from -752.26 mV at CPE to -304 mV at chitosan-Ag NPs/CPE, and then showing a surface controlled process with the catalytic rate constant (Kcat) of 0.125 × 10-3 M-1 s-1 and a coefficient of diffusion (D) of 2.20 × 10-6 cm2 s-1 with an enhanced current response. Under optimized conditions, the electro-catalytic reduction peak current of 4-NA increased linearly with increasing of 4-NA concentration over the range of 1 μM to 0.5 mM (R2 = 0.9866) with a detection limit of 0.86 μM (3 × Sb/P).