With the recent development of nanotechnology, enhancement of the stability of nanomaterials is becoming ever more important for their practical applications. We studied the silica-coating of Cu nanoparticles and the enhanced stability of silica-coated Cu nanoparticles to oxidation. The metallic nanoparticles are easily oxidized and agglomerated compared with the bulk metals because the nanoparticles possess large specific surfaces. The Cu nanoparticle is one of the most difficult nanoparticles to be handled due to its absence of the oxidation stability. In the synthesis of silica-coated Cu nanoparticles via a sol-gel process using tetraethyl orthosilicate, the addition of NH3 as a catalyst of sol-gel reaction yielded homogeneous silica-coating. However, a large amount of Cu nanoparticles is instantly dissolved by forming complex ions in a NH3 solution during and before the silica-coating process. This is the difficulty in the silica-coating of Cu nanoparticles. In the present work, the dissolution behavior of Cu nanoparticles was electrochemically examined. This electrochemistry-based optimization of reducing power of a reaction bath enabled us to synthesize the silica-coated Cu nanoparticle via a consecutive liquid-phase reaction which requires only basic equipment and involves no separate centrifuging or extraction step. Cu nanoparticles coated by silica shells had the remarkable stability even in the presence of a strong oxidizing agent. Furthermore, we demonstrated that the highly stable Cu nanoparticles can be applied to a red pigment using a unique red color of Cu nanoparticles because of its surface plasmon resonance.