Two series of Ni-doped CaCu₃Ti₄O₁₂ ceramics with CaCu₃Ti_4-4хNi_4хO_12-δ and CaCu_3-3хNi_3хTi₄O₁₂ compositions were obtained by the solid-phase synthesis method. The magnetic behavior of the samples in the range of 77–400 K was studied by magnetic dilution. For the first time the samples of both series were characterized by the spectroscopic methods: XPS and NEXAFS. As a result of XPS spectroscopy, it was found that calcium, copper and nickel atoms mainly have the oxidation state (II), and titanium atoms can exhibit oxidation states of (III) and (IV). NEXAFS-study of Ni-doped CCTO showed that titanium atoms mainly have the oxidation state (IV). In the NEXAFS spectra of nickel of the both series of the samples, a feature associated with the presence of Ni(II) in the square-planar environment was manifested. It was concluded that nickel atoms were distributed in the positions of copper and titanium in the samples of both series. The magnetic behavior of the nickel-doped solid solutions of both types of substitution was different only at x ≥ 0.03, which indicated the advantage of placing nickel (II) atoms in the Cu(II) position. According to the magnetic dilution data, the antiferromagnetic exchange was realized between the nearest paramagnetic nickel atoms in CaCu₃Ti_4-4хNi_4хO_12-δ and the ferromagnetic one between the paramagnetic clusters.