Reactions in water at ambient temperature and pressure between a lanthanide ion and benzene-1,3,5-tricarboxylate (or trimesate) lead to two series of iso-structural coordination polymers. Their general chemical formula is [Ln(tma)(H(2)O)(6)](∞) for the lightest lanthanide ions (Ln = La-Dy except Pm), while it is [Ln(tma)(H(2)O)(5)·3.5H(2)O](∞) for the heaviest ones (Ho-Lu plus Y). For the heaviest lanthanide ions, reactions at 50 °C lead to a third structural family with the general chemical formula [Ln(tma)(H(2)O)(3)·1.5H(2)O](∞) with Ln = Ho-Lu plus Y. Homo-lanthanide coordination polymers that belong to the latter two families do not exhibit luminescence in the visible region. Therefore, we used a phase induction strategy to obtain molecular alloys that belong to these structural families and show sizeable emission. The random distribution of the lanthanide ions over the metallic sites has been investigated using (89)Y and (139)La solid-state NMR spectroscopy experiments. Luminescent properties of homo- and hetero-nuclear coordination polymers based on Eu(3+) and Tb(3+) have been studied in detail and compared. As a result, this study strongly suggests that exchange-based intermetallic energy transfer mechanisms play an important role in these systems. It also suggests the presence of an intermetallic exchange pathway through π-stacking interactions.