In this paper, we demonstrate a simple, template-free, reproducible and one-step synthesis of hydrophilic KGdF(4): Ln(3+) (Ln = Ce, Eu, Tb and Dy) nanoparticles (NPs) via a solution-based route at room temperature. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) and cathodoluminescence (CL) spectra are used to characterize the samples. The results indicate that the use of water-diethyleneglycol (DEG) solvent mixture as the reaction medium not only allows facile particle size control but also endows the as-prepared samples with good water-solubility. In particular, the mean size of NPs is monotonously reduced with the increase of DEG content, from 215 to 40 nm. The luminescence intensity and absolute quantum yields for KGdF(4): Ce(3+), Tb(3+) NPs increase remarkably with particle sizes ranging from 40 to 215 nm. Additionally, we systematically investigate the magnetic and luminescence properties of KGdF(4): Ln(3+) (Ln = Ce, Eu, Tb and Dy) NPs. They display paramagnetic and superparamagnetic properties with mass magnetic susceptibility values of 1.03 × 10(-4) emu g(-1)·Oe and 3.09 × 10(-3) emu g(-1)·Oe at 300 K and 2 K, respectively, and multicolor emissions due to the energy transfer (ET) process Ce(3+)→ Gd(3+)→ (Gd(3+))(n)→ Ln(3+), in which Gd(3+) ions play an intermediate role in this process. Representatively, it is shown that the energy transfer from Ce(3+) to Tb(3+) occurs mainly via the dipole-quadrupole interaction by comparison of the theoretical calculation and experimental results. This kind of magnetic/luminescent dual-function materials may have promising applications in multiple biolabels and MR imaging.