Rare-earth doped GaN structures offer potential for optical devices emitting in the visible region [1,2]. We describe a study of MOVPE grown GaN-on-sapphire epilayers implanted with Europium ions, producing characteristic red emission lines between 540 and 680 nm due to intra-4f(n) electron transitions. As-implanted and subsequently annealed samples are investigated using a combination of wavelength dispersive x-ray analysis (WDX), electron microscopy, cathodoluminescence (CL) and photoluminescence (PL). WDX is shown to be a powerful technique for quantifying rare-earth concentrations in GaN, with varying electron beam voltages allowing a degree of depth profiling, further enhanced by the simultaneous collection of room temperature luminescence (CL) from the analysed region . The intensities of the sharp lines observed in the luminescence spectrum are compared to the doping density (between 1014 – 1015 cm−2) and the Eu content measured by WDX, using a Eu-doped glass standard. Differences observed in the luminescence spectra produced by laser and electron beam excitation will be discussed along with the importance of the annealing conditions, which “heal” defects visible in the electron micrographs.