Electrons emitted from the core levels of a photon-irradiated crystalline sample undergo scattering by atoms in the vicinity of the emitting species. Subsequent interference phenomena between the electron wave portions propagating to the detector produce intensity modulations as a function of the direction of detection. This process constitutes the physical basis of the angle-scanned X-ray photoelectron diffraction (XPD) technique. The resulting modulations, properly interpreted, are rich in structural information concerning the near-surface atomic layers. In this review, after an introduction to the principles of XPD, some selected results in the field of ultrathin epitaxial films will be reported in order to outline the merits of the technique. Qualitative structural information (e.g., growth modes and lattice distortions) is directly obtained from the experimental raw data without the need for theoretical simulation. On the other hand, quantitative structural parameters, as well as the presence of stacking faults and other structural defects, may be deduced by using a trial-and-error fitting procedure based on simple scattering models.