The homogeneity, solid solubility, and chemical bonds in the new materials PbTe, SnTe doped with Ce were investigated. Scanning electron microscope observation and electron probe microanalysis carried out on PbTe crystals doped with Ce, revealed three types of Ce-rich precipitates with following compositions: CeTe2, Ce3Te7, Ce2Te5 and small admixture of PbTe in precipitates. The solubility of Ce in PbTe matrix was estimated as 0.5+/-0.1 at.%. The solubility of PbTe in CeTe2 and Ce3Te7 was found to be 3+/-0.5 at.%, but 7+/-0.5 at.% in the case of Ce2Te5. In SnTe crystal doped with Ce only one kind of precipitate with composition Ce2SnTe5 was found. Cerium solubility in SnTe matrix was estimated to be 1+/-0.25 at.%. According to our knowledge this is the first report of the identification of Ce2SnTe5 compound. The similar compounds Ce2SnS5 and Ce2SnSe5 are known.