The growth, morphology, and structure of films on Cu(001) and Ag(001) are studied by means of low‐energy electron diffraction (LEED), medium‐energy electron diffraction, Auger electron spectroscopy, and scanning tunnelling microscopy. Different concentrations x from about 0.5 to 1 and thicknesses from 0.2 to 12.9 ML of are examined. For several values of x, exhibits a c(2 2) superstructure pattern on Cu(001) when the total thickness is around or above 0.5 ML. Above 1 ML, LEED patterns of can be only observed on Ag(001), but not on Cu(001). LEED‐I(V) is employed to deduce the vertical interlayer distance for as‐grown and post‐annealed films on Ag(001). Above 500 K, Ag from the substrate segregates into the films.