This paper addresses the structural characterisation of a series of U/Fe, U/Co and U/Gd multilayers. X-ray reflectivity has been employed to investigate the layer thickness and roughness parameters along the growth direction and high-angle diffraction measurements have been used to determine the crystal structure and orientation of the layers. For the case of uranium/transition metal systems, the interfaces are diffuse and the transition metals are present in a polycrystalline form of their common bulk phases with a preferred orientation along the closest packed planes; Fe, bcc (110) and Co, hcp (001), respectively. The uranium is present in a poorly crystalline orthorhombic, alpha-U state. In contrast, the U/Gd multilayers have sharp interfaces with negligible intermixing of atomic species, and have a roughness, which is strongly dependent on the gadolinium layer thickness. Diffraction spectra indicate a high degree of crystallinity in both U and Gd layers with intensities consistent with the growth of a novel hcp U phase, stabilised by the hcp gadolinium layers.