We propose a novel technique of integrating silica nanowires to carbon microelectrode arrays on silicon substrates. The silica nanowires were grown on photoresist-derived three-dimensional carbon microelectrode arrays during carbonization of patterned photoresist in a tube furnace at 1000 °C under a gaseous environment of N(2) and H(2) in the presence of Cu catalyst, sputtered initially as a thin layer on the structure surface. Carbonization-assisted nucleation and growth are proposed to extend the Cu-catalyzed vapor-liquid-solid mechanism for the nanowire integration behaviour. The growth of silica nanowires exploits Si from the etched silicon substrate under the Cu particles. It is found that the thickness of the initial Cu coating layer plays an important role as catalyst on the morphology and on the amount of grown silica nanowires. These nanowires have lengths of up to 100 µm and diameters ranging from 50 to 200 nm, with 30 nm Cu film sputtered initially. The study also reveals that the nanowire-integrated microelectrodes significantly enhance the electrochemical performance compared to blank ones. A specific capacitance increase of over 13 times is demonstrated in the electrochemical experiment. The platform can be used to develop large-scale miniaturized devices and systems with increased efficiency for applications in electrochemical, biological and energy-related fields.