BACKGROUNDSelf‐propagating high‐temperature synthesis was used to create mesoporous CeO2 and MgO powders as well as nanocomposites based on them for efficient degradation of organic dyes.RESULTSIt has been investigated how magnesium oxide and cerium oxide interact to affect the crystal structure, morphology and microstructure of the materials produced. It was assumed that CeO2 forms on the surface of MgO while the material's developed surface is preserved. The values of the specific surface area and average pore diameter of the studied samples depend on the composition and vary in the ranges of 16–41 m2 g−1 and 11.919 nm, respectively.CONCLUSIONIt has been established that the sizes of CeO2 crystallites in the composition of nanocomposites change insignificantly and range from 6.5 to 7.4 nm. The photocatalytic activity of the studied samples is at least two times higher compared to analogs. The samples MgO–CeO2 (30 mol%) and MgO–CeO2 (50 mol%) showed the maximum photodegradation efficiency of acid telon blue and direct bright blue dyes at levels of 98.5% and 92.5%, respectively. © 2023 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI).