The synthesis of BaC2O4·0.5H2O and its thermal decomposition to α-BaC2O4 and β-BaC2O4 was investigated. BaC2O4·0.5H2O is precipitated at room temperature from aqueous solutions of barium chloride and ammonium oxalate. The deuterated compound BaC2O4·0.5D2O was made in analogy with D2O as the solvent. The compounds were characterized by X-ray and neutron diffraction analysis. Single-crystal X-ray diffraction of BaC2O4·0.5H2O measured at 120 K gave the triclinic cell a = 8.692 (1), b = 9.216 (1), c = 6.146 (1) Å, α = 95.094 (3), β = 95.492 (3), γ = 64.500 (3)°, space group P\bar 1, Z = 4. Two independent Ba atoms are each coordinated to nine O atoms at distances from 2.73 (1) to 2.99 (1) Å. One of the two oxalate ions deviates significantly from planarity. The water molecule does form weak hydrogen bonds. In situ X-ray powder diffraction was used to study the thermal decomposition of BaC2O4·0.5H2O and the formation of α-BaC2O4. The X-ray powder pattern of α-BaC2O4 measured at 473 K was indexed on a triclinic cell with a = 5.137 (3), b = 8.764 (6), c = 9.006 (4) Å, α = 83.57 (4), β = 98.68 (5), γ = 99.53 (5)°, and the space group P\bar 1 with Z = 4.