The chemical composition of the natural arsenate-apatite mineral johnbaumite [nominally Ca10(AsO4)6(OH)2] and its alteration product hedyphane [Ca4Pb6(AsO4)6Cl2] have been determined by electron microprobe analysis and the structures of johnbaumite and synthetic Sr-, Ba- and Pb-arsenate apatites have been studied by As K-edge X-ray absorption spectroscopy and synchrotron X-ray powder diffraction. All samples belong to the holosymmetric apatite space group P63/m with As5+ substituted for P5+ in the tetrahedral structural site. Johnbaumite contains small amounts of F and Pb (∼0.9 and ∼4.4 wt.% respectively) and hedyphane has the ideal composition (formula given above); the compositions of these coexisting phases define the two limbs of a solvus occurring between Ca- and Pb-arsenate apatite end members. The unit-cell parameters and cation-oxygen bond lengths for the arsenate apatites studied are discussed alongside published data for end-member Ca-, Sr-, Ba- and Pb-phosphate apatite analogues with (OH), F, Cl or Br as the anions at the centres of the channels in the apatite structure. This discussion rationalizes the relationships between the two structural sites A(1) and A(2) occupied by divalent cations in terms of the size of the A-O polyhedra and the distortion of the A(1)-O polyhedron as measured by the metaprism twist angle [O(1)-A(1)-O(2) projected onto (001)].