In this thesis the growth and surface structure of ternary oxide nanolayers supported on single crystal metal surfaces have been experimentally investigated by modern surface analytic techniques, including scanning tunnelling microscopy (STM), low energy electron diffraction (LEED), x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) with laboratory and synchrotron radiation sources, and high-resolution electron energy loss spectroscopy (HREELS). For some of the studied systems the experimental results have been supported by density functional theory (DFT) calculations, performed in the group of Alessandro Fortunelli in Pisa, Italy, and by ex-situ x-ray diffraction (XRD) measurements, conducted in the group of Prof. Roland Resel at the Technical University in Graz. The major part of the thesis is focussed on the preparation of transition metal tungstates, such as MnWO4, NiWO4, and FeWO4, in two-dimensional (2D) form and the study of their novel structural properties. The preparation approach is based on a solid state reaction between structurally well-defined 2D binary oxide layers, pre-prepared on metal surfaces, and (WO3)3 clusters, deposited under ultrahigh vacuum (UHV) conditions. The reaction between a WO3 monolayer on Pd(100), whose structure was understood by the combined effort of experiment and theory, and metal atoms in oxygen atmosphere offered an alternative route for the preparation of well-ordered 2D MnWO4, NiWO4 and FeWO4 layers on Pd(100). All these layers were found to exhibit hexagonal surface structure, which is not present in their bulk MWO4 counterparts, but showing a similar building sequence of M-O-W-O layers. Epitaxial bulk-type NiWO4 films have been also grown on a Ni(110) surface, which expose two types of facets vicinal to the polar NiWO4(100) surface. It has been argued that this surface faceting, combined with a favourable epitaxial relationship to the metal substrate, are driven by the reduction of the polarity and the minimization of the surface and interface energies. In the monolayer regime a well-ordered wetting 2D NiWO4 layer forms on the Ni(110) surface, which is iso-structural to the 2D CuWO4 phase on Cu(110). In a slightly different direction, the growth and structure of ultrathin cerium oxide layers on Cu(110) have been investigated. Here also, the formation of a 2D ternary Cu4Ce4O12 layer is established, which is symmetry and lattice mismatched to the substrate and displaying a nanoscopic stripe pattern.