The cascade oxidative annulation reactions of aryl imidazoles with two molecules of alkynes via multiple C–H activation proceed efficiently in the presence of [Cp*RhCl₂]₂ and Cu(OAc)₂·H₂O to give substituted benzo[ij]imidazo[2,1,5-de]quinolizine-based polyheteroaromatic compounds. This method is compatible with various functional groups, which are very useful for further synthetic transformations.