The study is devoted to development of luminescent materials based on ZnO nanoparticles synthesized in polymer media by modified co-precipitation method using green chemistry principles. The polyvinyl alcohol (PVA) media have caused great impact on the absorption and luminescence properties of the synthesized ZnO-xPVA nanoparticles. Theoretical calculations of the electronic structure of ZnO crystals containing a set of point defects including Hi and Ci their combinations with Oi native defects were carried out. The density functional theory (DFT) band-periodic method within the super-cell approach was used to verify this assumption. Results of the calculations of the optical spectra were compared with spectral features of the samples, including low temperature and high energy excitations of the ZnO-xPVA nanoparticles.