Identification of products formed by the reaction of plutonium metal with liquid water at 23{degree}C indicates that the plutonium-oxygen phase diagram is similar to the cerium-oxygen and praseodymium-oxygen diagrams. Quantitative measurements of H{sub 2} formation and analytical data suggest that a sequence of hydrolysis reactions produces oxide hydrides of trivalent plutonium, Pu{sub 2}O{sub 3}, mixed-valent oxides and PuO{sub 2}. The intermediate oxides are the n {equals} 7, 9, 10 and 12 members of the Pu{sub n}O{sub 2n{minus}2} homologous series. Properties of the residue formed by thermal decomposition of the initial hydrolysis product, plutonium monoxide monhydride (PuOH), are consistent with the formation of metastable plutonium monoxide. Crystal-chemical, thermodynamic, and kinetic factors are evaluated, but definitive assignment of the equilibrium Pu-O diagram is not possible. 22 refs., 6 figs., 1 tab.