Photoluminescence spectra of high quality GaN epilayers, grown by MOCVD on sapphire substrates and implanted by isoelectronic ions: As, P, and Bi, were investigated. Post implant annealing was done at temperatures of up to 1150 °C, in a tube furnace under flowing NH3 or N2, and in a rapid thermal annealing system in ambient of N2. The PL of GaN: P annealed at 1150 °C in NH 3 exhibited strong pair-type modulated structures on the short wavelength shoulder of an emission band.The band at 2.914 eV is due to the recombination of bound exciton to P-hole isoelectronic traps (P-BE), and the modulated structure results from electron-hole recombination at pairs of neutral donors and a hole on P isoelectronic traps. The PL of GaN: As, GaN: Bi showed an emission with peaks at 2.597 eV and 3.241 eV, due to the recombination of an exciton bond to As and Bi isoelectronic-hole traps. We also studied thermal quenching excitation spectra, and PL kinetics. The experimental results are discussed using a simple spherical potential-well model for isoelectronic traps: As, P, and Bi replacing nitrogen in GaN.