The paper presents the results of a comprehensive study of the structural-phase composition, morphology, optical, luminescent, and scintillation characteristics of thick ZnO films fabricated by magnetron sputtering. By using a hot ceramic target, extremely rapid growth (~50 µm/h) of ZnO microfilms more than 100 µm thick was performed, which is an advantage for the industrial production of scintillation detectors. The effects of post-growth treatment of the fabricated films in low-temperature plasma were studied and a significant improvement in their crystalline and optical quality was shown. As a result, the films exhibit intense near-band-edge luminescence in the near-UV region with a decay time of <1 ns. Plasma treatment also allowed to significantly weaken the visible defect luminescence excited in the near-surface regions of the films. A study of the luminescence mechanisms in the synthesized films revealed that their near-band-edge emission at room temperature is formed by phonon replicas of free exciton recombination emission. Particularly, the first phonon replica plays the main role in the case of optical excitation, while upon X-ray excitation, the second phonon replica dominates. It was also shown that the green band peaking at ~510 nm (2.43 eV) is due to surface emission centers, while longer wavelength (>550 nm) green-yellow emission originates mainly from bulk parts of the films.