In this paper, we realize the liquid-phase chemical synthesis of high-quality orthorhombic polycrystalline BaMgF4: RE3+ (RE = Eu, Tb, Sm, Dy, Yb-Er/Tm) compounds with hydrothermal and high-temperature solution methods, respectively. The products from hydrothermal technology show the micrometer size while the products from hydrothermal technology present nanosheet morphology. The rare earth ions doped BaMgF4 from hydrothermal synthesis are discussed in details, which can realize the downconversion luminescence for doped Eu3+ or Tb3+ and upconversion luminescence for Yb3+/Er3+ (Tm3+), respectively. To our knowledge, the hydrothermal or high temperature solution synthesis and photoluminescence (Eu3+, Tb3+ or Yb3+/Er3+(Tm3+)) of these fluoride systems are firstly reported. (C) 2013 Elsevier Ltd. All rights reserved.