This paper reports on the structures and properties of Y1Ba2Cu3O9−x samples prepared in precisely controlled oxygen environments using a solid-state ionic technique. By titrating out oxygen at low temperatures, orthorhombic Y1Ba2Cu3O9−x samples were prepared with oxygen contents below 6.50. Resistivity and magnetometry studies indicated that these reduced, orthorhombic samples were marginally superconducting, with their superconductivity probably arising from local regions of higher oxygen content.