The formation of indium‐donor pairs (donors: P, As, Sb) in silicon is identified by perturbed angular correlation spectroscopy. After the electron capture decay of the111In probe atoms to111Cd, the electric field gradient (EFG) is measured at the corresponding cadmium‐donor pairs. For all three complexes a similar temperature dependence of the EFG is observed which can be explained quantitatively by a model based on the charge state of the cadmium‐donor acceptors. The corresponding energy levels are given.