This work is dedicated to the development of new types of composite thermoluminescent detectors based on the single crystalline films of Ce-doped GdAlO3 perovskite and Mn-doped YAlO3 and (Lu0.8Y0.2)AlO3:Mn perovskites as well as Ce and Pr-doped YAlO3 single crystal substrates. These detectors were obtained using the Liquid Phase Epitaxy growth method from the melt solution based on the PbO-B2O3 fluxes. Such composite detectors can by applied for the simultaneous registration of different components of mixed ionization fluxes using the differences between the thermoluminescent glow curves, recorded from the film and crystal parts of epitaxial structures. For creation of the new composite detectors, we considered using, for the film and crystal components of epitaxial structures (i) the different perovskite matrixes doped with the same type of activator or (ii) the same perovskite host with various types of activators. The thermoluminescent properties of the different types of epitaxial structures based on the abovementioned films and crystal substrates were examined in the conditions of β-particles and X-ray excitation with aim of determination of the optimal combination of perovskites for composite detectors. It was shown that, among the structures with all the studied compositions, the best properties for the simultaneous thermoluminescent detection of α- and X-rays were the GdAlO3:Ce film/YAlO3:Ce crystal epitaxial structure.