Volatile properties of copper(II) complexes of the general formula [Cu2(tBuNH2)2(μ‐O2CR)4] (R = CnF2n+1, n = 1–6) (1–6), and their potential application as CVD precursors are discussed. These compounds do not require special storage and handling conditions, and they are sources of metallated species between 435 and 473 K. Analysis of variable temperature infrared (IR) spectra of vapors prove the formation of the volatile and stable copper(I) carboxylate and copper(II) amine carboxylate species. Results of CVD experiments prove the usefulness of the CuII complexes studied in the production of metallic copper layers, between 673 K and 743 K, on silicon (Si(111)), Si‐SiO2, titanium, and Ti‐TiO2 substrates. Film morphologies are studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The structure and purity of copper layers are studied using X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and selected area electron diffraction (SAED).