BaLuF5:Ce,Tb,Eu(Sm) submicrospheres were synthesized via an ILs/ethylene glycol(EG) two-phase system. The crystalline phase, size, morphology, and luminescence properties were characterized using powder X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra. The results show that 1-methyl-3-octylimidazolium hexafluorophosphate ([Omim]PF6) was used as fluoride source and capping agent to tune morphology and size of the crystals. The formation mechanism has been supposed. Under the excitation of ultraviolet, the BaLuF5:5%Ce3+,5%Tb3+, BaLuF5:Eu3+, and BaLuF5:5%Ce3+,5%Sm3+ exhibit green and red emission, which was derived from Tb3+, Eu3+, and Sm3+ emission. When codoping Ce3+, Tb3+, Sm3+ or Eu3+ together, multi-color emission can be realized. Furthermore, this synthetic route may have potential applications for fabricating other lanthanide fluorides. (C) 2016 Elsevier Inc. All rights reserved.