X ray photoelectron diffraction (XPD) patterns of polar zinc oxide (ZnO) surfaces were investigated experimentally using hard x rays and monochromatized Cr Kα radiation and theoretically using a cluster model approach and a dynamical Bloch wave approach. We focused on photoelectrons emitted from the Zn 2p_3/2 and O 1s orbitals in the analysis. The obtained XPD patterns for the (0001) and (0001) surfaces of a ZnO single crystal were distinct for a given emitter and polarity. Polarity determination of c-axis-textured polycrystalline ZnO thin films was also achieved with the concept of XPD, even though the in-plane orientation of the columnar ZnO grains was random.