Abstract The short range structure of molten NaHSO4(I) and KHSO4(II) was estimated by X-ray diffraction. The polyatomic anion, HSO4-, in both molten salts was found to have a distorted tetrahedral structure in which the bond lengths of S-O and S-OH were 1.45 Å and 1.53 Å in (I) and 1.46 Å and 1.56 Å in (II), respectively. The coordination number of the Na+ or K+ around the HSO4- was evaluated to be about unity. The semi-empirical molecular orbital calculations by the MNDO-MOPAC method were applied to the determination of the intraionic structure of the H S 0 4 and the bond lengths of S-O and S -OH were computed to be 1.528 Å and 1.666 Å, respectively, supporting qualitatively that the HSO4- forms a rather distorted tetrahedron.