© 2019 by the authors. Photoluminescence properties of cubic zinc blende ZnO thin films grown on glass substrates prepared by the spray pyrolysis method are discussed. X-ray diffraction spectra show the crystalline wurtzite with preferential growth in the (002) orientation and a metastable cubic zinc blende phase highly oriented in the (004) direction. Raman measurements support the ZnO cubic modification growth of the films. Photoluminescence (PL) spectra of zinc blende films are characterized by a new PL band centerd at 2.70 eV, the blue emission, in addition there are two principal bands that are also found in hexagonal ZnO films with the peak positions at 2.83 eV and 2.35 eV. The origin of the 2.70 eV band can be attributed to transitions from Zn-interstitial to Zn-vacancies. It is also important to mention that the PL intensity of the 2.35 eV band of the zinc blende thin films is relatively higher than in the band present in hexagonal ZnO films, which means that zinc blende films have more oxygen vacancies, as was corroborated by means of the energy dispersion spectroscopy (EDS) measurements. PL spectra at 77 °K were measured and the 2.70 eV band was confirmed for the zinc blende films. Some PL bands of cubic films also appeared for the hexagonal phase, which is due, to a certain extent, to the similar ions stacking of both wurtzite and zinc blende symmetries.