Palladium(II) acetate is readily converted into Pd3(μ2‐OH)(OAc)5 (1) in the presence of water in a range of organic solvents and is also slowly converted in the solid state. Complex 1 can also be formed in nominally anhydrous solvents. Similarly, the analogous alkoxide complexes Pd3(μ2‐OR)(OAc)5 (3) are easily formed in solutions of palladium(II) acetate containing a range of alcohols. An examination of a representative Wacker‐type oxidation shows that the Pd‐OH complex 1 and a related Pd‐oxo complex 4 can be excluded as potential catalytic intermediates in the absence of exogenous water. When is palladium acetate not palladium acetate? Anywhere near trace amounts of water or alcohols. Palladium acetate is extremely sensitive to hydrolysis in solution and moderately so in the solid state. The resulting hydroxide complex is likely to be the true starting point for many reactions and catalytic processes that are reported as using palladium acetate.