The structure of pseudobinary Co‐Zr and Cu‐Zr metallic glasses, where Co and Cu were substituted by Fe, was studied by means of  57Fe‐Mo¨ssbauer spectroscopy. The resulting spectra can be divided into two different classes: (1) For Zr concentrations larger than 67 at. %, the structure of the glass, as derived from Mo¨ssbauer spectroscopy, is nearly independent from a substitution, leading to only small changes of the average isomer shifts and quadrupole splittings. These small variations of hyperfine parameters can be ascribed to charge transfer effects. (2) For lower Zr contents, pronounced systematic changes of hyperfine parameters occur upon Co or Cu substitution. Beyond changes of the average hyperfine values, the corresponding quadrupole‐splitting distributions become dependent on the degree of substitution, i.e., there is a concentration dependent splitting into two peaks. For the amorphous binary Zr‐Fe system, these two peaks have been connected to two amorphous phases with concentrations near Zr2Fe and ZrFe2. At least for the Fe‐doped Cu‐Zr metallic glasses it could be demonstrated that Fe does not substitute the Cu sites but rather creates preferred environments.