The synthesis, characterization, thermal decomposition, and full hydrolysis of Cu(I)2Zr2(OiPr)10 (1), Cu(I)4Zr4O(OiPr)18 (2), and Cu(II)4Zr4O3(OiPr)18 (3) are reported. Compound 1 is converted to compound 2 via hydrolysis. Species 1 and 2 are converted to 3 via oxidation with dioxygen. The molecular structure for 2 consists of two [Cu2(mu2-OR)2Zr2(mu2-OR)3(OR)4]+ fragments bound together via a pseudotetrahedron mu4-O2- ligand bridging the copper centers. The X-ray structure of 3 consists of a planar Cu4O(OiPr)24+ fragment capped by two Zr2O(OiPr)82-face-sharing bioctahedral units. The central oxo of the copper fragment is rigorously square-planar. Magnetic studies of 3 reveal a singlet ground state both in solution and the solid state. TGA studies of 1-3 reveal that all the systems undergo internal redox, producing copper metal, acetone, and H-2. The final products contained an increasing amount of zirconia with increasing number of oxo ligands in the precursor species. Full hydrolysis of 1 and 3, followed by thermolysis, produced Cu(O), Cu2O, and CuO with zirconia depending on thermolysis conditions. Results also indicate that precursor design influences the thermolysis behavior of the solid-state product.