In this paper, the synthesis of rare earth fluoride β-NaGdF 4 with multiform morphologies via a facile hydrothermal method has been fulfilled. The phases and shapes of the products can be tuned by changing the experimental parameters, including F − source and pH value of mother liquor. The morphologies for the products range from submicrorods, submicrospheres, dumbbell-like nanorods, cobblestone-like particles to aggregates constructed from nanoparticles. The results indicate that F − source and pH value play a critical role in determining the morphologies of the final products. Additionally, we investigate the photoluminescence (PL) properties of Ce 3+ /Ln 3+ (LnEu, Tb and Dy) codoped down-conversion (DC) and Yb 3+ /Er 3+ (Tm 3+ , Ho 3+ ) codoped up-conversion (UC) in β-NaGdF 4 host lattices. In the process of DC photoluminescence, energy transfer has occurred. This energy transfer occurs through the energy migration process like S→Gd 3+ →(Gd 3+ ) n →A (S represents the sensitizer and A represents the activator) and the Gd 3+ plays an intermediate role in the process.