We designed and successfully synthesized the silver vanadium oxides/polyaniline (SVO/PANI) triaxial nanowires by combining in situ chemical oxidative polymerization and interfacial redox reaction based on β-AgVO(3) nanowires. The β-AgVO(3) core and two distinct layers can be clearly observed in single triaxial nanowire. Fourier transformed infrared spectroscopic and energy dispersive X-ray spectroscopic investigations indicate that the outermost layer is PANI and the middle layer is Ag(x)VO((2.5+0.5x)) (x < 1), which may result from the redox reaction of Ag(+) and aniline monomers at the interface. The presence of the Ag particle in a transmission electron microscopy image confirms the occurrence of the redox reaction. The triaxial nanowires exhibit enhanced electrochemical performance. This method is shown to be an effective and facile technique for improving the electrochemical performance and stability of nanowire electrodes for applications in Li ion batteries.