Nitrate crystals reveal nonlinear optical properties and could be considered as converters of laser radiation in the short-wave region. The conditions for obtaining and basic properties of K2Ba(NO3)4 double nitrate crystals were investigated. Crystal growth was implemented by slow cooling in the temperature range of 72–49 °C and low rate evaporation. The structural analysis of K2Ba(NO3)4 formation on the basis of two mixed simple nitrate structures is discussed. The main groups of oscillations in K2Ba(NO3)4 crystal were revealed using Raman and IR spectroscopy, and the table of vibrations for this compound was compiled. The electronic structure of K2Ba(NO3)4 was elucidated in the present work from both experimental and theoretical viewpoints. In particular, X-ray photoelectron spectroscopy (XPS) was employed in the present work to measure binding energies of the atoms constituting the titled compound and its XPS valence-band spectrum for both pristine and Ar+ ion-bombarded surfaces. Further, total and partial densities of states of constituent atoms of K2Ba(NO3)4 have been calculated. The calculations reveal that the O 2p states dominate in the total valence-band region of K2Ba(NO3)4 except of its bottom, where K 3p and Ba 5p states are the principal contributors, while the bottom of the conduction band is composed mainly of the unoccupied O 2p states, with somewhat smaller contributions of the N 2p∗ states as well. With respect to the occupation of the valence band by the O 2p states, the present band-structure calculations are confirmed by comparison on a common energy scale of the XPS valence-band spectrum and the X-ray emission O Kα band for the K2Ba(NO3)4 crystal under study. Furthermore, the present calculations indicate that the K2Ba(NO3)4 compound is a direct-gap material.