Abstract: Holtite, (Si2.25Sb0.75)B[Al6(Al0.43Ta0.27□0.30)O15(O,OH)2.25], is orthorhombic a = 4.6914(5), b = 11.896(2), c = 20.383(4)Å, space group Pnma. Full-matrix least-squares refinement yielded a final R = 0.030, for 1664 reflections with I ⩾ 3σ(I). Its crystal structure is closely related to that of dumortierite, but with the difference that extensive substitution of Si by Sb occurs in holtite. SbO3 triangular pyramids replace the SiO4 tetrahedra arranged around the inside edge of the hexagonally shaped tunnels which are the feature of the dumortierite and holtite structures. Associated with these replacements is the replacement of Al by Ta in the octahedral site centred in these tunnels, and the development of vacancies in this metal site and its attached oxygens.