The crystal structure of killalaite has been approximately determined, using a crystal from the original locality. The ionic constitution is Ca_3+x (H_1–2xSi₂O₇) (OH), with x ≈ 0·2 for the crystal studied. Crystal data are: monoclinic pseudo cell with a 6·807, b 15·459, c 6·811 Å, β 97·76°, space group P2₁/m, Z = 4, D_x-ray = 2·94 gcm^-3. Additional, very weak reflections indicate a B-centred monoclinic true cell with doubled a and c. The structure was determined using only the pseudo cell reflections, and includes one fractionally occupied Ca site; the larger true cell possibly arises from ordering of Ca atoms in these sites, together with associated small shifts of other atoms. There are weak indications that the degree of occupancy of this site may be variable. The X-ray powder pattern has been indexed and a calculated pattern is also given. A synthetic compound called ‘Phase F’ by Aitken and Taylor (1960) appears identical with or closely similar to killalaite.