Rare earth/lithium complexes stabilized by ethylenediamine-bridged bis(phenolate) ligands have been synthesized and characterized. In addition to five rare earth/lithium amides isolated as major complexes, two other rare earth/lithium complexes bearing two phenolate ligands were also isolated. The activities of rare earth/lithium amides in catalyzing the amidation of aldehydes and amines were studied, which revealed that the yttrium/lithium complex was highly active for a wide range of substrates, generating 58 examples of amides in 42-99% yields under mild conditions (i.e., room temperature, 3-hour reaction time, additive-free). More importantly, this is the first example of rare earth-based catalysts capable of catalyzing the amidation of primary aliphatic amines.