Ce‐pyrochlore (CaCeTi2O7), is a chemical analogue for CaPuTi2O7, which is a proposed ceramic waste form for deposition of excess weapon‐usable Pu in geological repositories. Ce‐pyrochlore was synthesized by firing and annealing a mixture of Ce(NO3)4, TiO2, and Ca(OH)2 with a stoichiometry of CaCeTi2O7 at 1,300°C for 50 hours. The annealed product contains Ce‐pyrochlore, Ce‐bearing perovskite, CeO2 (cerianite), and minor CaO. Electron energy‐loss spectroscopy (EELS) was used to determine the valence of Ce in the synthesized materials using the shape of the Ce M4,5 edge. Cerium in the perovskite is dominated by Ce3+. The Ce4+/ΣCe in the pyrochlore is 0.8, giving (Ca0.87Ce0.203+Ce0.864+Ti0.05)Ti2O7. High‐resolution TEM images show that the boundary between pyrochlore and perovskite is semicoherently bonded. The orientational relationship between the neighboring pyrochlore and perovskite is not random. There are no glassy phases observed at the grain boundaries between pyrochlore and perovskite, and between C...