The structure of ultrathin silica films on Mo(112) has been investigated by grazing scattering of fast He atoms from the film surface. We discuss two recent experimental techniques which allow us to study the arrangements of surface atoms of these films in detail. The methods comprise: (i) classical rainbow scattering under axial surface channeling conditions; and (ii) fast atom diffraction. Our work demonstrates the attractive features of grazing fast atom scattering as a powerful analytical tool in studies on the structure of surfaces. From the analysis of our data we find a clearcut support for a structural model based on the arrangement of film atoms in terms of a 2D network. Copyright © 2010 John Wiley & Sons, Ltd.