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CaW is Zintl Phase structured and crystallizes in the tetragonal I4_1/amd space group. The structure is three-dimensional and consists of two CaW frameworks. Ca is bonded to four equivalent W atoms to form distorted corner-sharing CaW4 tetrahedra. All Ca–W bond lengths are 2.99 Å. W is bonded to four equivalent Ca atoms to form distorted corner-sharing WCa4 tetrahedra.
Ca3W crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Ca is bonded in a distorted see-saw-like geometry to four equivalent W atoms. There are two shorter (3.30 Å) and two longer (3.54 Å) Ca–W bond lengths. W is bonded to twelve equivalent Ca atoms to form a mixture of corner and face-sharing WCa12 cuboctahedra.