Photoluminescent poly(urethane-acrylate) (PUA) nanowires are designed and synthesized through copolymerization of a presynthesized-europium (Eu) complex with active vinyl groups and a vinyl functionalized PUA macromonomer matrix, initiated by azobisisobutyronitrile. This procedure provides a method to prepare PUA-Eu nanowires through in situ polymerization. Based on this, a series of PUA-Eu nanowires with diameters of 80-300 nm are successfully obtained in templates of anodized aluminum oxide by in situ polymerization. The obtained PUA-Eu nanowires display different morphologies such as sharp, round, and flat head by controlling the casting conditions. Furthermore, the PUA-Eu nanowires exhibit unique luminescence properties provided through Eu(III) elements, and the luminescence intensity significantly enhances with the increase in Eu complex concentration. PUA-Eu nanowires have longer fluorescence lifetimes than that of Eu complexes and PUA-Eu plates.