Unlike other 3d transition metal monoxides (MnO, FeO, CoO, and NiO), CuO is found in a low-symmetry distorted monoclinic structure rather than the rocksalt structure. We report here of the growth of ultrathin CuO films on SrTiO3 substrates; scanning transmission electron microscopy was used to show the stabilization of a tetragonal rocksalt structure with an elongated c-axis such that and the Cu-O-Cu bond angle , pointing to metastable six-fold coordinated Cu. X-ray absorption spectroscopy demonstrates that the hole at the Cu site for the CuO is localized in orbital unlike the well-studied monoclinic CuO phase. The experimental confirmation of the tetragonal structure of CuO opens up new avenues to explore electronic and magnetic properties of six-fold coordinated Cu. © Copyright EPLA, 2014.