The structure and properties of ternary oxide materials at the nanoscale are poorly explored both on experimental and theoretical levels. With this work we demonstrate the successful on-surface synthesis of two-dimensional (2D) ternary oxide, MnWO x and FeWO x , nanolayers on a Pd(1 0 0) surface and the understanding of their new structure and phase behaviour with the help of state-of-art surface structure and spectroscopy techniques. We find that the 2D MnWO x and FeWO x phases, prepared under identical thermodynamic conditions, exhibit similar structural properties, reflecting the similarity of the bulk MnWO4 and FeWO4 phases with the wolframite structure. Structure models of prototypical 2D ternary oxide phases are proposed and discussed in the light of new structure architecture concepts which have no analogues in the bulk.