The physical properties of an impurity atom in a semiconductor are primarily determined by the lattice site it occupies. In general, this occupancy can be correctly predicted based on chemical intuition, but not always. We report on one such exception in the dilute magnetic semiconductors Co- and Mn-doped ZnO, experimentally determining the lattice location of Co and Mn using β−-emission channeling from the decay of radioactive 61Co and 56Mn implanted at the ISOLDE facility at CERN. Surprisingly, in addition to the majority substituting for Zn, we find up to 18% (27%) of the Co (Mn) atoms in O sites, which is virtually unaffected by thermal annealing up to 900 °C. We discuss how this anion site configuration, which had never been considered before for any transition metal in any metal oxide material, may in fact have a low formation energy. This suggests a change in paradigm regarding transition-metal incorporation in ZnO and possibly other oxides and wide-gap semiconductors.