A collection of GdF3 core-shell structured (CSS) phosphors Were synthesized by hydrothermal method. The as prepared (AP) phosphors were coated with SiO2 layers to avoid aggregation and sintering during thermal annealing at 800 degrees C, after which the SiO2 layers were etched off and the annealed phosphors became highly dispersible. The annealed CSS phosphor aGdF(3):Eu3+@GdF3:Ce3+,Dy3+ shows excellent multicolor luminescence performance with the aid of dual-channel excitation and energy migration (EM) procedure of Gd3+ ions. By inserting pyromellitic acid (PMA) organic ligands into the interfaces between annealed core and AP shell layer regions, the so-called antenna effect of organic ligands of PMA forms a new excitation channel, which makes the CSS phosphora GdF3:Eu3+@PMA@GdF3:Ce3+,Dy3+ exhibit significantly enhanced multicolor luminescence via multi-channel excitation and EM process. The prepared CSS phosphors in this work are excellent candidates for applications in solid-state lighting.