The relative intensity, $\gamma = I(^{3}P)/I(^{1}P)$, of the group of X-ray emission Ti and Cr $K_{\alpha}L^{1}$-satellites in metals and their ion–covalent compounds is experimentally investigated. As established, the value of $\gamma$ decreases by 30–50% at the transition from metals, Ti and Cr, to carbides and oxides, TiC, Cr$_3$C$_2$, TiO$_2$, Cr$_2$O$_3$, with increasing of effective charge of metal atoms. The cause of the $\gamma$ value decreasing may be due to the dependence of the $KL_{2,3}(^{3}P){\varepsilon}p(^{2}S)$ and $KL_{2,3}(^{1}P){\varepsilon}p(^{2}S)$ configurations’ interaction on the screening of the $K$- and $L_{2,3}$-vacancies by free electrons. In metals, this screening substantially reduces the amplitudes of transitions between the states of the $KL_{2,3}(^{3}P){\varepsilon}p(^{2}S)$ and $KL_{2,3}(^{1}P){\varepsilon}p(^{2}S)$ configurations. In ion–covalent compounds, the screening is practically absent; so, a significant enhancement of the Coulomb interaction of the ejected 2$p$-electron with $L_{2,3}$-vacancy leads to a mixture of the $^{3}P$- and $^{1}P$ states of $KL_{2,3}$-configuration by means of the intense interchannel $KL_{2,3}(^{3}P){\varepsilon}p(^{2}S) \to KL_{2,3}(^{1}P){\varepsilon}p(^{2}S)$ transitions.