<p>Silver has been widely used in electronic components containing glass, such as inorganic ceramic substrates and inductors, due to its high conductivity. However, the diffusion of Ag⁺ into the glass during heat treatment, which can negatively affect electrical performance and compromise the device's reliability, presents a complex scientific challenge that requires further understanding. Here, the effects of different alkaline earth metal oxides on the structure of the silicate glass network and the inhibition of silver diffusion were investigated. The inhibitory performance against silver ion diffusion in sodium silicate glass increases in the order Mg²⁺ &lt; Ca²⁺ &lt; Ba²⁺ &lt; Sr²⁺. Impressively, Sr²⁺ ions with a weaker ionic field strength are more likely to generate non-bridging oxygen. These oxygen species effectively trap Ag⁺ by forming Ag–O bonds, consequently leading to the inhibition of silver diffusion. Therefore, this work provides valuable guidance for designing glass with robust resistance to Ag⁺ diffusion.</p>