Ce2TeO2 crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Ce3+ is bonded in a 4-coordinate geometry to four equivalent Te2- and four equivalent O2- atoms. All Ce–Te bond lengths are 3.49 Å. All Ce–O bond lengths are 2.35 Å. Te2- is bonded in a distorted body-centered cubic geometry to eight equivalent Ce3+ atoms. O2- is bonded to four equivalent Ce3+ atoms to form a mixture of edge and corner-sharing OCe4 tetrahedra.