Three types of β-NaYF4 nanoparticles, uncoated core (NaYF4:Yb/Ho/Ce), single-layer coated core@shell (NaYF4:Yb/Ho/Ce@NaYF4:Yb) and double-layer coated core@shell@shell (NaYF4:Yb/Ho@NaYF4:Yb@NaYF4:Yb) with Ce3+ doped in core, first and second shell, respectively, were synthesized through solvothermal method to investigate the cross-relaxation between Ho3+ and Ce3+ for the tunable upconversion luminescence. By doping Ce3+ into different layers with different doping concentrations, asystematically investigation on the tunable upconversion luminescence from green to red was conducted. The results show that a remarkable color tuning can be achieved from green to redwhen increasing the doping concentration of Ce3+ in the same layer of Ho3+.And if Ce3+ and Ho3+ are separated in different layers, the color tuning will be significantly depressed due to the reduced cross-relaxation between Ho3+ and Ce3+, which was confirmed by the investigation on the decay curves of Ho3+. The UC emission intensity of core@shell and core@shell@shell is significantly enhanced as compared with that of unmodified corenanoparticles.