The dependence of the critical current density Jc on hydrostatic pressure to 0.6 GPa is determined for a single 25 degrees [001]-tilt grain boundary in a bicrystalline ring of nearly optimally doped melt-textured YBa2Cu3Ox. Jc is found to increase rapidly under pressure at +20%/GPa. A new diagnostic method is introduced (pressure-induced Jc relaxation) which reveals a sizable concentration of vacant oxygen sites in the grain boundary region. Completely filling such sites with oxygen anions should lead to significant enhancements in Jc.