Na2TeO5 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(2) atoms. In the second Na site, Na(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(2) atoms. Te(1) is bonded to one O(1) and four equivalent O(2) atoms to form distorted TeO5 square pyramids that share corners with four equivalent O(2)Na2TeO trigonal pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Te(1) atom. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Te(1), and one O(2) atom to form distorted ONa2TeO trigonal pyramids that share  a cornercorner with one Te(1)O5 square pyramid, corners with five equivalent O(2)Na2TeO trigonal pyramids, and edges with two equivalent O(2)Na2TeO trigonal pyramids.
Na2TeO5 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(2) atoms. Both Na(1)-O(1) bond lengths are 2.11 Å. All Na(1)-O(2) bond lengths are 2.61 Å. In the second Na site, Na(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(2) atoms. All Na(2)-O(2) bond lengths are 2.40 Å. Te(1) is bonded to one O(1) and four equivalent O(2) atoms to form distorted TeO5 square pyramids that share corners with four equivalent O(2)Na2TeO trigonal pyramids. The Te(1)-O(1) bond length is 1.86 Å. All Te(1)-O(2) bond lengths are 2.19 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Te(1) atom. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Te(1), and one O(2) atom to form distorted ONa2TeO trigonal pyramids that share  a cornercorner with one Te(1)O5 square pyramid, corners with five equivalent O(2)Na2TeO trigonal pyramids, and edges with two equivalent O(2)Na2TeO trigonal pyramids. The O(2)-O(2) bond length is 1.50 Å.