Ca2Ag2O5 crystallizes in the orthorhombic Pbam space group. Ca(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(2), and three equivalent O(3) atoms. Ag(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ca(1) and two equivalent Ag(1) atoms to form OCa4Ag2 octahedra that share corners with four equivalent O(3)Ca3Ag2 trigonal bipyramids, edges with two equivalent O(1)Ca4Ag2 octahedra, and faces with four equivalent O(3)Ca3Ag2 trigonal bipyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Ag(1) atoms. In the third O site, O(3) is bonded to three equivalent Ca(1) and two equivalent Ag(1) atoms to form OCa3Ag2 trigonal bipyramids that share corners with two equivalent O(1)Ca4Ag2 octahedra, corners with six equivalent O(3)Ca3Ag2 trigonal bipyramids,  an edgeedge with one O(3)Ca3Ag2 trigonal bipyramid, and faces with two equivalent O(1)Ca4Ag2 octahedra. The corner-sharing octahedral tilt angles are 54°.
Ca2Ag2O5 crystallizes in the orthorhombic Pbam space group. Ca(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(2), and three equivalent O(3) atoms. Both Ca(1)-O(1) bond lengths are 2.63 Å. Both Ca(1)-O(2) bond lengths are 2.45 Å. There are a spread of Ca(1)-O(3) bond distances ranging from 2.48-2.57 Å. Ag(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. The Ag(1)-O(1) bond length is 2.09 Å. There is one shorter (2.06 Å) and one longer (2.41 Å) Ag(1)-O(2) bond length. Both Ag(1)-O(3) bond lengths are 2.07 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ca(1) and two equivalent Ag(1) atoms to form OCa4Ag2 octahedra that share corners with four equivalent O(3)Ca3Ag2 trigonal bipyramids, edges with two equivalent O(1)Ca4Ag2 octahedra, and faces with four equivalent O(3)Ca3Ag2 trigonal bipyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Ag(1) atoms. In the third O site, O(3) is bonded to three equivalent Ca(1) and two equivalent Ag(1) atoms to form OCa3Ag2 trigonal bipyramids that share corners with two equivalent O(1)Ca4Ag2 octahedra, corners with six equivalent O(3)Ca3Ag2 trigonal bipyramids,  an edgeedge with one O(3)Ca3Ag2 trigonal bipyramid, and faces with two equivalent O(1)Ca4Ag2 octahedra. The corner-sharing octahedral tilt angles are 54°.