Spectra of photoluminescence (PL) and X-ray excited luminescence (XRL) in region of 1.5-5.5 eV, PL excitation spectra using synchrotron radiation (3.7-22 eV), time-resolved impulse cathode-luminescence (ICL) spectra, the temperature depending of the XRL, decay kinetics as well as thermoluminescence curves were measured for single crystals Rb2KTiOF5, a promising nonlinear optical material. Single crystals are transparent in microwave, visible and near UV range, inter-band transition energy is Eg = 4.2 eV. Crystalline structure has two disordered mixed position O/F, phase transition in the region of 215 K. All the obtained results indicate that in luminescence spectra nonelementary band 2.2 eV is connected to the emission of self-trapped excitons. Nonelementary band 2.2 eV associated with the presence local distortion in the octahedron TiOF5. It is observed that at interband excitation in VUV region at energies more than 3.5 Eg the effect of multiplication of electronic excitations appears. That determines the high output of XRL and ICL. Luminescence methods of quality control of grown crystals are proposed.