Multivariate terbium-complexes were incorporated into polyacrylonitrile (PAN) and electrospun into flexible multifunctional nanofibers with a uniform diameter of similar to 200nm. Fluorescence comparison in multi-ligand-binding nanofibers under ultraviolet (UV) radiation verifies that the differentiated beta-diketone ligands with dual functions are the primary cause of the spectral fluctuation, adequately illustrating the available methods for the quantification of intermolecular reciprocities between organic ligands and central Tb3+ ions. Especially under 308nm UVB-LED pumping, the total emission spectral power of supramolecular Tb-complexes/PAN nanofibers are identified to be 2.88 mu W and the total emission photon number reaches to 7.94x10(12)cps which are nearly six times higher than those of the binary complex ones in the visible region, respectively. By modifying the sorts of organic ligands, the luminous flux and luminous efficacy of multi-ligand Tb-complexes/PAN nanofibers are up to 1553.42 mu lm and 13.72 mlm/W, respectively. Efficient photon-releasing and intense green-emission demonstrate that the polymer-capped multi-component terbium-complexes fibers have potential prospects for making designable flexible optoelectronic devices.