Applications of the techniques of normal-incidence x-ray standing wave (NIXSW) and medium-energy ion scattering (MEIS) to the elucidation of the structure of an ultrathin metallic film, Co on Cu(111), are reported. NIXSW and MEIS are shown to yield valuable and complementary information on the structure of such systems, yielding both the local stacking sequence and the global site distribution. For the thinnest films of nominally two layers, the first layer is of entirely fcc registry with respect to the substrate, but in the outermost layer there is significant occupation of hcp local sites. For films up to 8 monolayers (ML) thick, the interlayer spacing of the Co layers is 0.058±0.006Å smaller than the Cu substrate (111) layer spacing. With increasing coverage, the coherent fraction of the (1¯11) NIXSW decreases rapidly, indicating that the film does not grow in a fcc continuation beyond two layers. For films in this thickness range, hcp-type stacking dominates fcc twinning by a ratio of 2:1. The variation of the (1¯11) NIXSW coherent fraction with thickness shows that the twinning occurs close to the Co/Cu interface. For thicker films of around 20 ML deposited at room temperature, medium-energy ion scattering measurements reveal a largely disordered structure. Upon annealing to 300 °C the 20-ML films order into a hcp structure.