The influence of synthesis conditions on the formation of yttrium aluminum garnet (YAG) powders starting from the same solution precursors was investigated by employing a citrate–nitrate gel combustion process and a precursor plasma spraying technique. YAG powders were formed at ≥500 °C, through the citrate–nitrate gel combustion process, without any intermediate phase formation. Time-resolved x-ray experiments were performed for the first time on these citrate–nitrate precursor materials to understand their mode of decomposition. The in situ data confirmed a single-step conversion to YAG from the precursor powder without any intermediate phase formation. Ex situ experiments also produced similar results. However, the use of the same citrate–nitrate precursor solution as a liquid feedstock material in the precursor plasma spraying technique revealed an entirely different transformation mechanism to YAG through intermediate phases like H–YalO3 and O–YalO3.