We have identified the surface polar structure of wurtzite-type ZnO films by coaxial impact-collision ion scattering spectroscopy. High-quality ZnO epitaxial films were prepared on sapphire (alpha-Al2O3) (0001) substrates by laser molecular beam epitaxy using a ZnO ceramic target. The (000 (1) over bar) crystallographic plane (the O face) was found to terminate the top surface of the ZnO film by comparing spectra of the films with those of well-defined (0001) and (000 (1) over bar) surfaces of bulk single crystals. The preferential [000 (1) over bar] growth direction of ZnO films is discussed from the viewpoints of the chemical interaction at the interface and surface stability against sublimation.