Intrinsic emission of complex oxides with perovskite structure was analyzed in the undoped single crystal (SC) and single crystalline films (SCF) of YAlO 3 (YAP) using the time-resolved luminescence spectroscopy under excitation by synchrotron radiation. In contrast to bulk SC the YAP SCF are characterized by much lower concentration of YAl antisite and vacancy-type defects, which contribute to the intrinsic emission of YAP SC. Such a difference comes mainly from much lower temperature of the film growth using the Liquid Phase Epitaxy. For this reason, comparison of YAP SC and SCF appears very useful to study the nature of the intrinsic emission of perovskites consisting mainly of the exciton and defectrelated luminescence.1 Introduction The nature of intrinsic emission of oxides with the perovskite ABO 3 structures is still not clearly understood. The perovskites are complex oxides with two cation sublattices. The A cations are distributed over the octahedral position formed by six oxygen ligands whereas B cations are located in the voids between the octahedrons created by the twelve nearest oxygen ions. The intrinsic UV luminescence of these compounds was mainly investigated for the case of YAlO 3 perovskites (YAP) and usually consists of two or more bands in the UV region [1][2][3][4]. The positions and intensities of these bands depend on the method of material preparation, type and concentration of host defects [3,4].To clarify the nature of the intrinsic luminescence bands in YAP, various models have been proposed [1][2][3][4]. In earlier papers [1,2], the UV YAP emission in the bands at 5.9 and 4.0 eV was related to the decay of self-trapped excitons (STE) with the hole component, which is localized on the single-and twocharged oxygen ions in the form of О -and О 2 3-centers, respectively. At the same time due to high temperature crystallisation from melt usually in the oxygen-free atmosphere and existence of two cation sublattice the YAP single crystals (SC) always possess a certain concentration of the Y Al antisite defects (AD), as well as the vacancy-type defects (VD), first of all, the oxygen vacancies [5]. It was shown [6,7] that Y Al AD as analogues of the cation isoelectronic impurities in complex oxides, for instance, in garnets, create the emission and trapping centers, which contribute to the intrinsic luminescence of these compounds. Oxygen vacancies usually create the sites for one-or two-electron capture in the form of F + (V O¯) and F(V O ) centers which also contribute to the intrinsic emission of YAP SC [4,8]. Therefore, it is demanding to study the intrinsic luminescence of perovskites with different concentrations of such defects. The SC grown from melt with high concentration of AD and VD, and single crystalline films (SCF) of the same composition grown from melt-solution (MS) using Liquid Phase Epitaxy (LPE) offer