Pure copper metal thin films were grown on SiO2/Si(100) substrates by metal–organic (MO) CVD in a horizontal cold-wall reactor employing the two metal–organic compounds, Cu(OCHMeCH2NR2)2, where R = Et (1) and R = Me (2) as precursors. Thermogravimetric analyses proved them to be convenient compounds for the deposition of copper without a reducing agent. Depositions were carried out at various substrate temperatures in the range 230–350 °C. X-ray diffraction (XRD) indicated that the resulting films were highly crystalline and showed a strong (111) preferred orientation, which increased with increasing deposition temperature. Photoelectron spectroscopy (XPS) revealed that copper films deposited at 230 °C and 260 °C consisted solely of metallic copper with no detectable carbon, nitrogen, or oxygen contamination. Copper films obtained from 1 at 260 °C had a resistivity of 2.16 μΩ cm.