Nanoscale phosphors of Yb3+/Er3+/Tm3+-doped GdPO4 with different morphologies were synthesized using the solvothermal method with annealing at 750 °C and 1000 °C. A high concentration of Yb3+(35%mol) ions was successfully doped in the powders. Crystal structures were characterized through powder XRD measurement and Fourier transform infrared spectroscopy. SEM images have shown that the morphologies of the samples can be controlled by adjusting the pH value during their synthesis. Upconversion luminescence was investigated under 980 nm diode laser excitation. The upconversion processes were assessed on the basis of the power dependence of upconversion emission intensity. The light colour was investigated with respect to the 1931 CIE diagram. The samples show good emission tunability by monitoring the annealing temperature and the diode laser pump intensity. By properly adjusting the excitation power, white upconversion luminescence can be attained. Yb3+/Er3+/Tm3+-doped GdPO4 nanophosphors appear, which have potential applications in the field of upconversion-based white lighting devices.