In this paper, we present a facile and environmentally-friendly hydrothermal process to synthesize BaGdF5: 2.5 mol% Ce3+/2.5 mol% Ln(3+) (Ln = Sm, Dy, Eu and Tb) nano/submicroparticles. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), as well as photoluminescence (PL) spectra are used to characterize the resulting samples. The size, shape, and composition of the products could be tuned just by varying the organic additives and the pH values of the initial reaction solutions. The morphologies for the products include nanospheres, submicrospheres, peanut-like particles, as well as the spindle-like and star-like aggregates. Moreover, the size of the samples can be tuned from 50 nm to 150 nm. Additionally, we systematically investigate the luminescence properties of different lanthanide ions in BaGdF5 host. Under single-wavelength excitation at 260 nm, the samples doped with different lanthanide ions show intensive multicolor visible emissions depending on the doped Ln(3+) ions. The luminescence process can be attributed to the strong absorption of UV irradiation by Ce3+ ions, followed by energy transfer to Gd3+ ions, from which the energy is transferred to Ln(3+), resulting in the emission from the luminescent Ln(3+) centers. The Gd3+ ions play an intermediate role in this process.