We study the chemical shift of three different Cu atoms in YBa2Cu3O6.5, and compare the results with the formally mono-, di-, and trivalent model compounds Cu2O, CuO, and NaCuO2. We find similar chemical shifts between Cu in the empty chains, Cu in the planes, and Cu in the intact chains as between the Cu atoms in the model compounds. This suggests that the different Cu atoms in YBa2Cu3O6.5 have formal valences of approximately 1,2, and 3. © 1992 The American Physical Society.