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Ag2SeO4 crystallizes in the orthorhombic Fddd space group. The structure is three-dimensional. Ag1+ is bonded in a 6-coordinate geometry to six equivalent O2- atoms. There are a spread of Ag–O bond distances ranging from 2.35–2.79 Å. Se6+ is bonded in a tetrahedral geometry to four equivalent O2- atoms. All Se–O bond lengths are 1.69 Å. O2- is bonded in a 1-coordinate geometry to three equivalent Ag1+ and one Se6+ atom.
Ag2SeO3 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent Ag1+ sites. In the first Ag1+ site, Ag1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Ag–O bond distances ranging from 2.39–3.06 Å. In the second Ag1+ site, Ag1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Ag–O bond distances ranging from 2.33–2.80 Å. Se4+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There is two shorter (1.74 Å) and one longer (1.75 Å) Se–O bond length. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to four Ag1+ and one Se4+ atom. In the second O2- site, O2- is bonded in a 5-coordinate geometry to four Ag1+ and one Se4+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to three Ag1+ and one Se4+ atom.