Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a] pyridine derivatives were developed. These methods include the following: (ⅰ) Cu(Ⅱ) salts were used as metal sources and N, N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes. (ⅱ) An iodidecontaining compound was utilized as a ligand and iodide source to prepare complexes. An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated. (ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives, producing polydentate ligand scaffolds. Eight complexes were prepared and characterized. The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated. With the exception of complex 4, the remaining seven complexes all showed high catalytic activity. The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.