NaMnF3:Yb,Er and NaMnF3:Yb,Er@NaGdF4:xEu (x = 0, 0.3, 0.6, and 0.9) samples were synthesized by a simple hydrothermal method. The as-obtained NaMnF3:Yb,Er particles show a single red emission under the irradiation of infrared light (980 nm), due to the energy exchange transfer process between Mn2+ ions and Er3+ ions. Notably, further growth of NaGdF4:Eu on the basis of NaMnF3:Yb,Er enhanced the green up-conversion luminescence of Er3+ ions, which gradually shifted from red to green with the increase of the Gd3+ ion doping amount. In addition, NaMnF3:Yb,Er@NaGdF4:Eu exhibits red color under ultraviolet excitation (397 nm). These results provide a possible means for controlling the luminescence properties of the lanthanide doped up-conversion system. The luminescent film synthesized with NaMnF3:Yb,Er@NaGdF4:Eu can show different luminescent colors under different light irradiation (near infrared and ultraviolet), which indicates that they have potential applications in multi-mode anti-counterfeiting.