This study investigates the structure and electronic properties of the A‐center in Si1−xGex alloys (x = 0, 0.25, 0.50, 0.75, and 1), using the Heyd–Scuseria–Ernzerhof hybrid functional. It is found that the most stable structures form SiOSi bonds, with the other two atoms surrounding the A‐center being Ge atoms, which form a long bond between them. The behavior of the O atoms is significantly influenced by the Ge content. As it increases, the position of the O atom shifts relative to the surrounding atoms, thereby affecting the bond lengths and angles. The formation energy of the A‐center first decreases with increasing Ge content up to 0.75, which enhances the defect production; however, then it decreases from 0.75 to 1, thus suppressing defect production. The calculations are consistent with the experimental data, showing that the distance of the defect level from the conduction band minimum increases with Ge content, supporting the observed enthalpy changes in electron ionization.