A study of the subsolidus region of the BaO-La2O3-V 2O5 phase diagram has been carried out. Four ternary phases can be prepared, one of which has not been previously identified. The four ternary phases are a palmierite solid solution Ba3-3xLa2x V2O8, Ba2LaV3O11, BaLa10V4O26 (new phase) and Ba3La 40V12O93. Addition of BaLa10V 4O26 and the previously omitted phase La1.42V 0.58)3.58 to the ternary system has resulted n a re-determination of the complete phase diagram. A comprehensive study of the Ba3-3xLa 2xV2O8 solid solution has been carried out, employing a number of techniques including x-ray diffraction, infra-red spectroscopy, thermogravemetric analysis, impedance spectroscopy, electron paramagenetic resonance spectroscopy, inductively coupled plasma mass spectroscopy and x-ray absorption near edge structure spectroscopy. Conductivity measurements show the end-member Ba3V2O8 to be an oxide ion conductor, with the conduction mechanism being facilitated by the ease of transformation of the BaO3 layers to BaO2 and vice versa. The La-doped members show an increase in conductivity, with electrons becoming the dominant conducting species. The crystal structure of Ba2LaV 3O11 was confirmed to be isostructural with Ba2BiV 3O11. A full refinement of the structural parameters has been performed. The unit cell is primitive monoclinic, a = 12.44510(3)A, b = 7.78854(12)A, c = 11.26245(21)A and beta = 103.134(4)°, space group P21/c. Preliminary structural studies have begun on the new phase BaLa10V4O26. The x-ray powder pattern has been fully indexed and a possible monoclinic unit cell of a = 20.2939A, b = 5.886A, c = 12.6234A and beta = 118.05° is proposed. The serendipitous synthesis of a barium-deficient celsian phase, Ba0.8A11.6 Si2.4O8, is reported; the structure was solved using Patterson methods. The phase has a monoclinic unit cell with, a = 8.6090(8)A, b = 13.0858(12)A, c = 7.2047(7)A and beta = 115.418(2)°, space group C2/m.