We report the results of surface characterizations of niobium samples electropolished together with single cell cavities. These witness samples were located in three regions of the cavity, namely at the equator, the iris and the beam-pipe. Auger electron spectroscopy (AES) was utilized to probe the chemical composition of the topmost four atomic layers. Scanning electron microscopy with energy dispersive x-ray for elemental analysis (SEM/EDX) was used to observe the surface topography and chemical composition at the micrometer scale. A few atomic layers of sulphur (S) were found covering the samples non-uniformly. Niobium oxide granules with a sharp geometry were observed on every sample. Some Nb-O granules appeared to also contain sulphur.