Access to removable nanocomposite electrodes for electrosensing of pollutants is of great importance. However, the preparation of reproducible and reliable carbon electrodes decorated with metallic nanoparticles, a prerequisite for trustworthy devices, remains a challenge. Here we describe an innovative and easy method to prepare such electrodes. These latter are silicon-coated with a thin carbon film on which controlled silver nanostructures are grafted. Different silver nanostructures and surface coverage of the carbon electrode (16, 36, 51, and 67%) can be obtained through a careful control of the time of the hydrogenolysis of the N–N′ isopropyl butylamidinate silver organometallic precursor (t = 1, 5, 15, and 60 min, respectively). Importantly, all nanocomposite surfaces are efficient for the electrodetection of 4-nitrophenol with a remarkable decrease of the overpotential of the reduction of such molecule up to 330 mV. The surfaces are characterized by atomic force microscopy, grazing incidence X-ray diffraction, scanning electronic microscopy, and Raman spectroscopy. Furthermore, surface-enhanced Raman scattering effect is also observed. The exaltation of the Raman intensity is proportional to the surface coverage of the electrode; the number of hot spots increases with the surface coverage.