A series of aminophenolate and aminonaphtholate homoleptic zinc complexes were obtained using a simple and unique synthetic strategy. A rigorous analysis of the byproduct supported modifications of the main course of the bis-chelation reaction. Controlled alcoholysis was followed by alternation and controlled anaerobic hydrolysis of ethyl-zinc aminophenolate or aminonaphtholate complexes. This new and intriguing reaction yielded a new class of zinc corona complexes. All the synthesized complexes were fully characterized in the solid state and in solution using X-ray and spectroscopic methods as well as density functional theory calculations.