A K-10 montmorillonite catalyzed microwave-assisted oxidative coupling of amines is described. Substituted benzylamines readily undergo self-coupling reactions to produce benzylidene-benzylamines, while aliphatic amines and anilines cannot form self-coupled products. A mixture of a benzylamine and an aniline or aliphatic amine, respectively, effectively, and selectively produces mixed imines, such as benzylidene-anilines and benzylidene-alkylamines. (C) 2007 Elsevier Ltd. All rights reserved.