Two　coordination　complexes　(Eu2Eu4III)-Eu-II(OH)(4)(bza)(4)L-2　(1)　and　Eu-5(III)(H2O)(OH)(4)(NO3)(3)(bza)(4)L　(2)　have　been　assembled　with　the　tetrasubstituted　cyclen　ligand　N,N,N,N-tetrakis(2-hydroxy-3-methoxy-5-methylbenzyl)-1,4,7,10-tetraazacyclododecane　(H4L)　and　the　auxiliary　ligand　benzoic　acid　(Hbza).　Complex　2　is　a　pentanuclear　Eu-III　cluster　whereas　complex　1　is　a　huge　heterovalent　2Eu(II)/4Eu(III)　cluster　in　which　two　divalent　europium　ions　are　trapped　within　the　macrocyclic　cavities　of　the　designed　ligands　L　and　are　further　isolated　from　the　environment　by　peripheral　phenyl　rings　and　the　tetrahedral　4Eu(III)　cluster,　which　results　in　the　enhanced　oxidative　stability　of　Eu2+.　The　luminescence　of　complex　1　was　investigated　and　is　discussed　in　comparison　with　the　luminescence　of　ligand　H4L　and　complex　2.　Owing　to　the　protection　of　Eu2+　by　the　macrocyclic　ligands　L,　the　heterovalent　complex　exhibits　a　strong　broad　emission　band　with　a　maximum　at　533　nm　as　well　as　the　characteristic　sharp　emissions　of　Eu3+.　The　broad　emission　is　redshifted　compared　with　that　of　ligand　H4L　and　has　been　attributed　to　the　Laporte-allowed　4f(6)5d(1)4f(7)　transition　of　Eu2+.