The intensity of Eu-related luminescence from ion-implanted GaN with a 10nm thick AlN cap, both grown epitaxially by metal organic chemical vapor deposition (MOCVD) is increased markedly by high-temperature annealing at 1300°C. Photoluminescence (PL) and PL excitation (PLE) studies reveal a variety of Eu centers with different excitation mechanisms. High-resolution PL spectra at low temperature clearly show that emission lines ascribed to D05-F27 (∼622nm), D05-F37 (∼664nm), and D05-F17 (∼602nm) transitions each consist of several peaks. PL excitation spectra of the spectrally resolved components of the D05-F27 multiplet contain contributions from above-bandedge absorption by the GaN host, a GaN exciton absorption at 356nm, and a broad subedge absorption band centred at ∼385nm. Marked differences in the shape of the D05-F27 PL multiplet are demonstrated by selective excitation via the continuum/exciton states and the below gap absorption band. The four strongest lines of the multiplet are shown to consist of two pairs due to different Eu3+ centers with different excitation mechanisms.