We have demonstrated the first observable case of efficient energy transfer from poly-ligands to terbium ions through cross-linked siloxane in solution. The intensification of green luminescence was easily perceived by the naked eye under UV-254 nm illumination, where even the terbium dopants reached 0.1 μM. Moreover, the nano-scale fibrous structure (diameter 100–200 nm) aggregated to a micro-meter size round plate (diameter 1.1 μm). In addition, compound 1 equipped with three long tetradecyl chains in gels gained more of an advantage over the doubly tetradecylated compounds 2 and 3 in terms of energy migration to terbium ions due to side chain effects.