Prussian Blue nanoparticles (Fe4[Fe(CN)6]3 NPs) coated with several kinds of materials have been the focus of intense research due to their numerous applications in biomedicine, (bio)sensors, diagnosis, catalysis, etc. In this work, Fe4[Fe(CN)6]3 NPs coated with amino-functionalized silica, Fe4[Fe(CN)6]3@SiO2-NH2, were obtained regarding the principles of the sol-gel process. Structural, spectroscopic characterization and electrochemical properties of the hybrid nanomaterial (Fe4[Fe(CN)6]3@SiO2-NH2) were performed by X-ray diffraction (XRD), electronic and vibrational spectroscopy in UV-Vis, Fourier Transformation Infrared (FTIR) and cyclic voltammetry, respectively. The electronic spectrum of Fe4[Fe(CN)6]3@SiO2-NH2 exhibited a bathochromic shift to 798 nm when compared to the intervalence band absorption from Fe4[Fe(CN)6]3 species (690 nm), which was occasioned by coating SiO2 and groups NH2.The FTIR spectrum for Fe4[Fe(CN)6]3@SiO2-NH2 showed main bands (CN, Si-O-Si, CH, NH2, stretchings and deformations) characteristics of Prussian blue complex, silica and aminopropyl groups. Cyclic voltammogram for Fe4[Fe(CN)6]3@SiO2-NH2 exhibited two defined redox couples assigned to the conversion of FeII-FeIII (mixed valence) to FeII-FeIII (reduced form) and FeII-FeIII to FeIII-FeIII (oxidized form), respectively. It was observed an increased reversibility for the system and current intensities reduction after coating with silica. We envisage that nanomaterial developed can find applications in (bio)sensors and covalent imobilization of several biomolecules being of interest for biomedicine area.