A template-based strategy was developed which combines a wet-chemical technique and electrodeposition within nanoporous membranes. Morphological, structural and chemical characterization by means of electron microscopy and related techniques demonstrate unambiguously that coaxial nickel/poly(p-phenylene vinylene) (PPV) nanowires have been successfully synthesized. Moreover, modification of their optical and magnetic properties due to the nanoscale and the core–shell structure has been studied. The nickel-PPV nanowires exhibit a slightly blueshifted photoluminescence (PL), which is directly related to the tubular morphology of the PPV shell. The effect of the nickel core on the PL intensity of the PPV shell is discussed. The ferromagnetic behavior has been shown with the magnetization easy axis along the wire axis. These arrays of coaxial semiconducting polymer–metal nanowires embedded in a polymer membrane are interesting for flexible electronics and photovoltaic devices. Furthermore, their magnetic manipulation has been demonstrated, which opens the way to use them as multifunctional building blocks for bio-applications.