Scanning-tunneling microscopy and density-functional theory have been employed to identify the spatial correlation between an oxygen vacancy and the associated Ce(3+) ion pair in a defective CeO(2)(111) film. The two Ce(3+) ions can occupy different cationic shells around the vacancy. The resulting variation in the chemical environment leads to a splitting of the filled Ce(3+) f levels, which is detected with STM spectroscopy. The position of the Ce(3+) ion pair is reflected in characteristic defect patterns observed in empty-state STM images, which arise from the bright appearance of Ce(4+) ions next to the defect while the Ce(3+) remain dark. Both findings demonstrate that at least one excess electron localizes in a Ce ion that is not adjacent to the O vacancy.