NaYF₄:Yb³⁺/Tb³⁺ and NaYF₄:Yb³⁺/Tm³⁺ double doping fluoride nanomaterials with different doping concentrations were prepared by hydrothermal synthesis. In these materials, the Yb³⁺ was used as sensitizer to assist in luminous, Tb³⁺ and Tm³⁺ were added to the matrix sodium yttrium fluoride as activators of luminous center. The morphology and luminous properties of NaYF₄:Yb³⁺/Tb³⁺ and NaYF₄:Yb³⁺/Tm³⁺ nanoparticles were investigated by scanning electron microscope (SEM), X-ray diffraction andfluorescence spectrum. The X-ray diffraction patterns of the series of samples well match the NaYF₄ standard card. Upconversion luminescence spectra of materials under 980 nm laser excitation were obtained and the mechanism was also analyzed. Excited by 980 nm laser, the emission spectra of NaYF₄:Yb³⁺/Tb³⁺ including blue, green and red light, which correspond to the radiative transition of ⁵D₄→⁷F₆, ⁵D₄→⁷F₅, ⁵D₄→⁷F₁, respectively. The strong 480 nm emission can be seen in NaYF₄:Yb³⁺/Tm³⁺ excited by 980 nm laser, corresponding to the electron transition energy band of ¹G₄→³H₆. A strong red light emission band centered at 660 nm is corresponding to the ¹G₄→³F₄ energy level transition.