We have characterized as-grown and thermally treated YBaCuO single crystals by ESR, Raman spectroscopy, magnetic susceptibility, X-ray and neutron diffraction measurements. The as-grown crystals are tetragonal and are superconducting with an onset temperature of 30 K. They show an ESR signal which behaves as a localized Cu²⁺ ion with tetragonal symmetry and presumably originates from copper chain atoms that are octahedrally coordinated by six oxygen neighbors. The temperature dependence of the ESR between 150 and 270 K shows paramagnetic behavior and also dynamical features. Below 90 K, the ESR signal disappears reversibly. A likely explanation is that the onset of local superconductivity frustrates the spins responsible for the ESR signal.