Successful doping and excellent optical activation of Eu(3+) ions in ZnO nanowires were achieved by ion implantation. We identified and assigned the origin of the intra-4f luminescence of Eu(3+) ions in ZnO by first-principles calculations to Eu-Oi complexes, which are formed during the nonequilibrium ion implantation process and subsequent annealing at 700 °C in air. Our targeted defect engineering resulted in intense intrashell luminescence of single ZnO:Eu nanowires dominating the photoluminescence spectrum even at room temperature. The high intensity enabled us to study the luminescence of single ZnO nanowires in detail, their behavior as a function of excitation power, waveguiding properties, and the decay time of the transition.