The synthesis of a series of lanthanide tetracyanoplatinates containing the auxiliary ligands 1,10′-phenanthroline (phen) or 2,2′-bipyridine (bpy) have been carried out by reaction of Ln 3+ nitrate salts with phen or bpy and potassium tetracyanoplatinate in solvent systems containing dimethylsulfoxide and dimethylformamide. The use of these solvents has lead to the isolation of [{Ln(DMSO) 2 (C 12 H 8 N 2 )(H 2 O) 3 } 2 Pt(CN) 4 ](Pt(CN) 4 ) 2 ·2C 12 H 8 N 2 ·4H 2 O (Ln=Eu (Eu-1), Tb (Tb-1), Yb(Yb-1)), [Ln(DMF) 3 (C 12 H 8 N 2 )(H 2 O) 2 NO 3 ]Pt(CN) 4 (Ln=La (La-2), Eu (Eu-2), Tb (Tb-2)), and [Ln(DMF) 3 (C 10 H 8 N 2 )(H 2 O) 2 NO 3 ]Pt(CN) 4 (Ln=La (La-3), Sm (Sm-3), Eu (Eu-3), Tb (Tb-3)) in the form of single crystals. Single-crystal X-ray diffraction has been used to investigate their structural features. The use of DMSO versus DMF as the solvent results in markedly different structural features. Eu-1 contains [{Eu(DMSO) 2 (C 12 H 8 N 2 )(H 2 O) 3 } 2 Pt(CN) 4 ] 2+ complex cations where the two Eu 3+ centers are linked by a trans-bridging Pt(CN) 4 2− anion to form a dimeric lanthanide complex cation. An additional uncoordinated Pt(CN) 4 2− anion balances charge. Eu-2 and Eu-3 consist of zero-dimensional salts with [Eu(DMF) 3 (C 12 H 8 N 2 )(H 2 O) 2 (NO 3 )] 2+ or [Eu(DMF) 3 (C 10 H 8 N 2 )(H 2 O) 2 (NO 3 )] 2+ complex cations, respectively, and only non-coordinated Pt(CN) 4 2− anions. Photoluminescence measurements illustrate that the Eu 3+ and Tb 3+ compounds for all three structure types display enhanced emission due to intramolecular energy transfer from the coordinated cyclic amines.