Single crystals of Ln 3GaO 6 (Ln = Nd, Sm, Eu, Gd) were grown out of a reactive high temperature hydroxide melt. The structures were solved by single-crystal X-ray diffraction. These gallium oxides crystallize in the polar space group Cmc2 1 where the orientation of the GaO 4 tetrahedra determines the polarity of the structure. The atomic positions along with the determination of the absolute structure are reported. The lanthanide atoms are located in a seven-fold coordination environment forming edge-sharing zigzag-chains. The photoluminescence was investigated and the europium and gadolinium members of this series exhibit intense luminescence in the visible portion of the spectrum.