The atomic geometry and growth mechanism of Fe films (0.5-20 monolayers (ML)) epitaxially grown on Ni(001) have been investigated by a multitechnique approach with the twofold aim of assessing the reliability of quick structural techniques (primary-beam diffraction modulated electron emission (PDMEE), secondary electron imaging (SEI)), suitable for on-line monitoring of film growth, and studying the structural evolution of the Fe/Ni system. To this end, samples were analyzed by PDMEE and SEI together with synchrotron radiation photoelectron diffraction (PD), and extended x-ray absorption fine structure (EXAFS). Results show the effectiveness of the approach by quick techniques. In the early stage of growth, Fe arranges in a strained fcc(001) structure. Transition to the bcc phase occurs through nucleation of bcc(110) domains with the bcc〈111〉//fcc〈110〉 orientation. Quantitative analysis based on PD and EXAFS data is also presented.