The structure of metallic alloys and multilayers prepared by pulsed laser deposition using KrF radiation (248 nm) and a pulse duration of 30 ns was investigated by X-ray diffraction. In comparison with conventional deposition techniques, the structural properties of laser-deposited Fe-Nb and Fe-Ag films can be characterized by the formation of amorphous or metastable nanocrystalline phases with higher solubilities, unusually enlarged lattice spacings in the growth direction and different film textures. Often these films are in a state further away from the equilibrium state than sputtered or evaporated samples, Fe/Nb multilayers exhibit much broader amorphous interfaces, while Fe/Ag superlattices shaw a different texture and sharp interfaces visible by satellite reflections in the X-ray spectra. These differences can be understood by the about 10(5) times higher instantaneous deposition rate and the high kinetic energy of the deposited particles in the range of up to 100 eV.