Luminescence studies were conducted on tetracyanoplatinate complexes that contain up to four different ligands simultaneously, resulting in very complex structural features. Most of the complexes of (terpy)-Eu-platinum tetra cyanide complexes (terpy = terpyridine) crystallize with low one-, and two-dimensional structural types. Herein we present studies of several of these coordination compounds where variation of the counter anion results in a drastic change in their photoluminescence properties. The effect of anion variation on the intramolecular energy transfer (IET) mechanism will be discussed in detail. The complexes with nitrate and triflate counter anions display a highly efficient energy transfer from dual donors to an acceptor Eu3+ ion. The excited energy donors in these systems are the organic ligand (terperidine) and the platinum tetracyanide ion. Both species are directly coordinated to the acceptor cation. When the counter anion is changed to the acetate ion, the bonding interaction between the platinum tetracyanide and Eu3+ is removed, and the energy transfer pathway is blocked. As a result, the donor emits strongly, albeit totally quenched in the complexes with direct bonding interaction. Moreover, all of these complexes show interesting structural features that consist of channels capable of accommodating volatile organic compounds. Details of the photoluminescence studies will be presented.