The thermal chemistry of copper(II)acetylacetonate, Cu(acac)2, on Ni(110) and Cu(110) single-crystal surfaces was probed under vacuum by using x-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Some data for acetylacetone (Hacac, CH3COCH2COCH3) adsorbed on Ni(110) are also reported as reference. Chemical transformations were identified in several steps covering a temperature range from 150 K to at least 630 K. The desorption of Hacac and a 3-oxobutanal (CH3COCH2CHO) byproduct was observed first at 150 and 180 K on Ni(110) and at 160 and 185 K on Cu(110), respectively. Partial loss of the acetylacetonate (acac) ligands and a likely change in adsorption geometry are seen next, with the possible production of HCu(acac), which desorbs at 200 and 235 K from the nickel and copper surfaces, respectively. Molecular Cu(acac)2 desorption is observed on both surfaces at approximately 300 K, probably from recombination of Cu(acac) and acac surface species. The remaining copper atoms on the surface lose their remaining acac ligands to the substrate and become reduced directly to metallic copper. At the same time, the organic ligands follow a series of subsequent surface reactions, probably involving several C–C bond-scissions, to produce other fragments, additional Hacac and HCu(acac) in the gas phase in the case of the copper surface, and acetone on nickel. A significant amount of acac must nevertheless survive on the surface to high temperatures, because Hacac peaks are seen in the TPD at about 515 and 590 K and the C 1s XPS split associated with acac is seen up to close to 500 K. In terms of atomic layer deposition processes, this suggests that cycles could be design to run at such temperatures as long as an effective hydrogenation agent is used as the second reactant to remove the surface acac a- Hacac. Only a small fraction of carbon is left behind on Ni after heating to 800 K, whereas more carbon and additional oxygen remains on the surface in the case of Cu.