Hexagonal gadolinium fluorides doped with Ce3þ ions and co-doped with Sm3þ,Eu3þ,Tb3þ or Dy3þ were successfully synthesized via a simple co-precipitation approach, in the presence of glycerin as a capping agent. These fluorides, as solids or in aqueous solutions, showed intense, multicolored luminescence depending on the lanthanide ions used. The structures of the products were confirmed by powder X-ray diffraction (XRD). The morphologies of the synthesized nanophosphors were examined using transmission electron microscopy (TEM). The TEM results showed that the crystallites had shapes that varied with the dopant ion used. The spectroscopic properties: excitation spectra, emission spectra and luminescence decays were recorded and studied in detail. Bright luminescences from all of the products were triggered by effective energy transfer between the ions embedded in their structures. The mechanism for this phenomenon was also proposed. All of the synthesized products formed stable aqueous colloids, exhibiting brightly multicolored luminescence under UV light irradiation.