The paper is concerned with the description of the physical nature of the dependence of the sputtered-atoms’ ionization probability on the atomic and electronic structures of a metal target bombarded with ions of neutral gases (matrix effect). A systematic analysis of the literature data and results of authors of this review is carried studying the secondary ion emission (SIE) of pure metals, dilute solid solutions, and concentrated alloys. The practical importance of such studies is because the phenomenon of renewable energy is the basis of a unique method of chemical, isotope as well as physical and chemical analysis not only of metallic materials, but of semiconductors and organic substances too. The high sensitivity of SIE to the change in the forces of interatomic interaction and the parameters of the electronic structure is revealed. Experimental and theoretical studies in this direction have made it possible to deepen the knowledge of the nature of the phenomenon of secondary ion emission that arises when metal targets are bombarded with inert-gas ions, and to outline ways for further studying and applying this phenomenon for diagnostics of solid surfaces and bulks. Particularly, the method of mass-spectrometry of secondary ions based on the SIE can be used to study the phase equilibrium diagrams as well as the first and second kind phase transformations. Taking into account the high sensitivity of SIE to the change in the forces of interatomic interaction and the parameters of the electronic structure, further investigations should be aimed at establishing stricter correlations between these properties of the material and such characteristics of SIE as the emission coefficient and the ionization probability of sputtered atoms. The solution of this problem will create a new quantitative method for determination of the binding energy of various atoms in the composition of multicomponent materials.