A spray-flame reaction step followed by a short 1-h sintering step under O₂ atmosphere was used to synthesize nanocrystalline cubic Al-doped Li₇La₃Zr₂O₁₂ (LLZO). The as-synthesized nanoparticles from spray-flame synthesis consisted of the crystalline La₂Zr₂O₇ (LZO) pyrochlore phase while Li was present on the nanoparticles' surface as amorphous carbonate. However, a short annealing step was sufficient to obtain phase pure cubic LLZO. To investigate whether the initial mixing of all cations is mandatory for synthesizing nanoparticulate cubic LLZO, we also synthesized Li free LZO and subsequently added different solid Li precursors before the annealing step. The resulting materials were all tetragonal LLZO (I4₁/acd) instead of the intended cubic phase, suggesting that an intimate intermixing of the Li precursor during the spray-flame synthesis is mandatory to form a nanoscale product. Based on these results, we propose a model to describe the spray-flame based synthesis process, considering the precipitation of LZO and the subsequent condensation of lithium carbonate on the particles' surface.