In this paper, the surface properties of bare and film-covered gallium nitride (GaN) of the wurtzite form, (0001) oriented are summarized. Thin films of several elements—manganese, nickel, arsenic and antimony—are formed by the physical vapour deposition method. The results of the bare surfaces as well as the thin film/GaN(0001) phase boundaries presented are characterized by X-ray and ultraviolet photoelectron spectroscopies (XPS, UPS). Basic information about electronic properties of GaN(0001) surfaces are shown. Different behaviours of thin films after post-deposition annealing in ultrahigh vacuum conditions, such as surface alloying, subsurface dissolving and desorbing, are found. The metal films form surface alloys with gallium (NiGa, MnGa), while the semi-metal (As, Sb) layers easily evaporate from the GaN(0001) surface. However, the layer in direct contact with the substrate can react with it modifying the surface properties of GaN(0001).