Interleaved low-energy electron diffraction (LEED) and magneto-optical Kerr effect (MOKE) measurements were carried out for room-temperature epitaxially grown FCC-like Fe/Cu(1 0 0) in the temperature range of 120–400 K. The structure of the Fe film was found to be not only dependent on thickness, as was believed previously, but also to be influenced by the temperature. Temperature-driven structural transitions were observed in the 4 and 4.5 ML films, this effect being more pronounced at 4 ML thickness. Whereas the whole 4 ML film assumes an FCC-like structure with a strong tetragonal expansion (FCT-like) at temperatures below 313 K, the bulk of the film relaxes into the ‘isotropic’ FCC-like structure and only the top layers remain expanded at temperatures above 333 K. Because only the FCT-like (expanded) Fe possesses ferromagnetic properties, the film becomes paramagnetic after heating above 333 K. This finding represents a new type of magnetic order-disorder transition and explains the lower value of the Curie temperature in the 4 ML Fe film as compared to 3 ML. In the 4.5 ML Fe film the similar correlation between the temperature-driven structural transition and an occurrence of the ferromagnetic long-range order was observed. Additionally, a pronounced difference in the energy positions of the characteristic maxima in the LEED I( E) curves for the (0 0) beam as well as a kinematic analysis of these curves imply a difference in the value of the tetragonal expansion for the entirely expanded FCC-like Fe film and the film expanded only in the topmost layers.