Polycrystalline fine powders of yttrium aluminate doped with Ce3+ were synthesised by spray pyrolysis of a polymeric precursor, which was obtained by dissolving the corresponding nitrates in a solution of ethylenediaminetetraacetic acid (EDTA) in ethylene glycol (EG). Aerosol decomposition was performed at 550 °C followed by an additional thermal treatment (900–1100 °C). The yield of either a single yttrium aluminium perovskite (YAP) phase or a single yttrium aluminium garnet (YAG) phase was investigated as a function of the predefined yttrium/aluminium ratio, the cerium doping concentration, the processing temperature, and the thermal-treatment regime, which included the variation of the heating and cooling rates (dT/dt), the residence tim...