Abstract Ceramic samples with the following composition (wt %): 50 TiO 2 , 10 CaO, 10 MnO 2 , 5 Al 2 O 3 , 5 Fe 2 O 3 , 10 ZrO 2 , 10 Ln 2 O 3 (Ln = La, Ce, Nd, Ho) or 10 СеО 2 , were studied by X-ray photoelectron spectroscopy. According to the data of X-ray phase analysis and scanning electron microscopy, they consist of murataite, zirconolite, and perovskite. In smaller quantities there are crichtonite, pyrophanite-ilmenite, and rutile. Ce 3+ dominates in cerium samples: the Ce 3+ : Ce 4+ ratio is 3 : 1 and does not depend on the method of adding the element to the charge—in the form of СeО 2 or Се 2 О 3 . All ceramics are dominated by Fe 3+ , its fraction is 92–94 rel %, while manganese is represented only by Mn 3+ cations.