The photoluminescence, its temperature dependences, as well as structural characteristics obtained by the method of Scanning electronic microscopy (SEM) have been studied in ZnO:Ag nanorods prepared by the ultrasonic spray pyrolysis (USP). PL spectra of ZnO:Ag NRs in the temperature range from 10 K to 300 K are investigated. Three types of PL bands have been revealed: i) the near-band-edge (NBE) emission, ii) defect related emission and iii) IR emission. It is shown that IR emission corresponds to the second-order diffraction of near-band-edge (NBE) emission bands. The study of NBE PL temperature dependences reveals that the acceptor bound exciton (ABE) and its second-order diffraction peak disappeared at the temperature higher than 200 K. The attenuation of the ABE peak intensity is ascribed to the thermal dissociation of ABE with appearing a free exciton (FE). The PL bands, related to the LO phonon replica of FE and its second-order diffraction, dominate in the PL spectra at room temperature that testify on the high quality of ZnO:Ag films prepared by the USP technology.