The strategy of layer-by-layer (LbL) self-assembly and calcining has been employed to prepare Au/TiO2 core/sheath nanowires. Ordered arrays were achieved by using an LbL assembly of cationic polyelectrolytes and inorganic precursors on template-grown Au nanowires. The wires were investigated with SEM, TEM, and X-ray energy dispersion analysis. The prepared composite nanowires were found to possess anatase porous sheaths of TiO2 with face-center-cubic polycrystallite An cores. The assembly strategy will be useful in fabricating core/sheath nanowires. The first reported core/porous-sheath nanowire is expected to be an ideal nanostructure for chemical sensors and photocatalysis due to its composite and highly porous structure.