This paper describes the effect of solvent‐induced synthetic routes of aluminium pendant oxazoline‐amido‐phenolate complexes. Treatment of ligand precursor L with AlMe3 in a 1:1 ratio in diethyl ether yielded the four‐coordinated complex (LAlMe)2. Reaction of ligand precursor L with AlMe3 in a 1:2 ratio in hexane generated the four‐coordinated complex L(AlMe2)2. A novel transformation mode occurred from L(AlMe2)2 to (LAlMe)2 when using diethyl ether or tetrahydrofuran as solvent. A density functional theory computational study also supports a plausible mechanism. All results were supported by spectroscopic data and in agreement with single‐crystal X‐ray diffraction structural analysis.