Cerium addition plays an important role in sintering, transformation and phasicochemical properties of cordierite ceramics. The present work aims at studying the distribution of Ce4+ in cordierite ceramics and its effect on the structure of cordierite crystal by means of differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electronic microscope (SEM) so as to clarify the behavior of Ce4+. Results show that Ce4+ can exist in two forms of CeO2 particles and solid solution in Ce4+ -modified cordierite ceramics by the sol-gel method. The CeO2 particles separately distribute in the cordierite matrix. Ce4+ dissolves little into cordierite crystal, resulting in a decrease of lattice constants ofthe crystal. This kind of distribution behavior of Ce4+ makes us to easily tailor the properties of the cordieritc ceramics.