The purpose of this study is to investigate the crystalline structure and optical properties of (GaZn)(NO) powders prepared by solid-state reaction between GaOOH and ZnO mixture under NH3 gas flow. While ammoniation of the GaOOH and ZnO mixture successfully produces the single phase of (GaZn)(NO) solid solution within a GaOOH rich composition of under 50 mol% of ZnO content, this process also produces a powder with coexisting (GaZn)(NO) and ZnO in a ZnO rich composition over 50 mol%. The GaOOH in the starting material was phase-transformed to α-, β-Ga2O3 in the NH3 environment; it was then reacted with ZnO to produce ZnGa2O4. Finally, the exchange reaction between nitrogen and oxygen atoms at the ZnGa2O4 powder surface forms a (GaZn)(NO) solid solution. Photoluminescence spectra from the (GaZn)(NO) solid solution consisted of oxygen-related red-emission bands and yellow-, green- and blue-emission bands from the Zn acceptor energy levels in the energy bandgap of the (GaZn)(NO) solid solutions.