A new, very efficient excitation mechanism of Yb intrashell 4f‐4f emission in ZnS is reported. We show that the energy transfer from donor‐acceptor pairs to Yb sites leads to Yb ionization (Yb3+⇒Yb2+), followed by capture of ionized carriers via the Yb3+ external excited state (bound exciton state), an energy transfer to the Yb3+ 4f shell, and Yb3+ 4f‐4f radiative recombination. Since three centers (donor, acceptor, and Yb) participate in the energy transfer process in which Yb is first ionized, the above excitation mechanism is of three‐center Auger transition nature. A similar excitation mechanism is expected for Eu, Sm, and Tm in ZnS, i.e., for these rare earth (RE) ions which can change their charge state from 3+ to 2+ in this lattice. For wider band‐gap sulfides, such as CaS or SrS, this mechanism can be of importance also for other REs, such as, for example, Pr, Dy, and Er.