In this study, GaN powders were synthesized from gallium oxide-hydroxide (GaOOH) through an ammonification process in an NH3 flow with the variation of B2O3 additives within a temperature range of 300-1050 oC. The additive effect of B2O3 on the hexagonal phase GaN powder synthesis route was examined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transformation infrared transmission (FTIR) spectroscopy. With increasing the mol% of B2O3 additive in the GaOOH precursor powder, the transition temperature and the activation energy for GaN powder formation increased while the GaN synthesis limit-time (tc) shortened. The XPS results showed that Boron compounds of B2O3 and BN coexisted in the synthesized GaN powders. From the FTIR spectra, we were able to confirm that the GaN powder consisted of an amorphous or cubic phase B2O3 due to bond formation between B and O and the amorphous phase BN due to B-N bonds. The GaN powder synthesized from GaOOH and B2O3 mixed powder by an ammonification route through β-Ga2O3 intermediate state. During the ammonification process, boron compounds of B2O3 and BN coated β-Ga2O3 and GaN particles limited further nitridation processes.