Spontaneous generation of complex order in apparently simple systems is both arresting and potentially useful. Here we describe the appearance of complex, ordered structures induced by the buckling of thin metal films owing to thermal contraction of an underlying substrate. We deposit the films from the vapour phase on a thermally expanded polymer (polydimethylsiloxane, PDMS). Subsequent cooling of the polymer creates compressive stress in the metal film that is relieved by buckling with a uniform wavelength of 20-50 micrometres. The waves can be controlled and orientated by relief structures in the surface of the polymer, which can set up intricate, ordered patterns over large areas. We can account qualitatively for the size and form of the patterned features in terms of the non-uniform stresses developed in the film near steps on the polymer substrate. This patterning process may find applications in optical devices such as diffraction gratings and optical sensors, and as the basis for methods of strain analysis in materials.