This work explores thermally modified AlF3 microstructures synthesized via aluminum-zinc reaction in hydrofluoric acid. Brief heating produces cushion-like morphologies, while room-temperature growths results in cracked crystals. The thermally treated samples exhibit anisotropic brittleness and easy delamination, suggesting weak interlayer bonding. SEM-EDS and XRD analyses reveal structure-property relationships, offering insights for tailored AlF3 microstructures in electronics and nanomaterials.