We report evidence that the body-centered cubic (bcc)-face-centered cubic (fcc) transition that occurs during Ni film growth on a Fe(001) substrate is preceded by a pre-martensitic phase, as demonstrated by low-energy electron diffraction. The corresponding film superstructure is characterized by a displacement of Ni atoms along the main 100 crystallographic axes of iron, without any rotation of the unit cell with respect to the (001) plane, in contrast with the martensitic transition that shows four fcc Ni domains with the Ni 211 crystallographic directions aligned with the Fe 110 axes. In addition, the martensitic transition is detected not at 6 ML, as previously believed, but above 20 ML if the Ni sample is rigorously kept at room temperature. The surface morphology of the bcc-fcc transition is characterized by the development of Ni mounds oriented along the 110 directions, as shown by scanning tunneling microscopy.