New compounds of the type REBa(2)VO(4)F(4) where RE = Y, Eu and Sm have been prepared for the first time by reacting REBa(2)VO(6) with NH4HF2 used as a low-temperature fluorinating agent. Thermogravimetric analysis/differential thermal analysis, chemical analysis, Eu-151 Mossbauer and EPMA evidence for the formation of the fluorinated compound is presented.