In this thesis, the magnetic and structural properties of layered epitaxial film systems and clusters are presented. A main achievement is the investigation of the direct correlation between magnetism and structural or morphological details of ultrathin films. For this purpose, the film structure has been accessed directly by means of surface science methods. The effect of structural changes on the magnetism were observed in-situ by magneto-optical techniques. First, epitaxial Fe films grown at low temperature (∼ 120K) on Cu(100) have been investigated. Such layers assume an fcc-crystal structure due to their interaction with the underlying Cu substrate. Within this work it is shown that the morphology of these films can be altered by annealing treatments. The thermally-induced morphological changes have direct consequences for domain wall propagation and result in increased coercivity and in modified surface anisotropy. Flat fcc-Fe layers on Cu(100) have been used as templates to form fcc-Fe/Cu/Fe trilayers with coupled perpendicular magnetization. Such systems might be of relevance for data storage applications. The perpendicular coupling is ascribed to the realignment of the magnetization of the bottom Fe layer within the stray field produced by the top Fe layer magnetization. The magnetic coupling has been investigated as a function of the thickness of the top and the bottom Fe layer as well as the Cu spacer thickness. It was found that the magneto-static interaction is a direct consequence of the fcc-structure of both Fe layers and the interface roughness. It is demonstrated that Fe films with fcc-structure and perpendicular magnetization can also be prepared on other fcc-templates, such as Pt substrates. Monatomic steps on the substrate surface are exploited to steer the growth of the film and with it the magnetism. Despite significant differences in the morphology and the atomic structure of Fe films on flat Pt(111) and stepped Pt(997), the critical thickness for the spin reorientation transition is similar on the two surfaces. However, the local atomic arrangement above three monolayer film thickness determines in-plane easy magnetization axis parallel to the step edges. For all layered systems investigated in this thesis, epitaxial strain is a the driving force which influences the film structure and triggers structural transitions. The strain dependence of the morphology and the magnetism was probed by a comparative study of Fe deposited on Pt substrates with and without a noble gas buffer layer. The formation of relaxed Fe clusters during Xe layer desorption is favored in the absence of the overlayer-substrate interaction. Striking differences in the magnetic anisotropy between the systems are attributed to magneto-elastic contributions. Measurements of the blocking temperature of the Fe clusters allow estimating the cluster size. All samples have been investigated under ultra high vacuum conditions. The study of the sample magnetic properties study was done by in-situ magneto-optical Kerr effect measurements and Kerr microscopy. Structural characterization was done by low energy electron diffraction and, in collaboration with other scientists, by scanning tunnelling microscopy.