The crystal chemistries of synthetic mimetite, Pb(10)(As(5+)O(4))(6)(Cl(2 - x)O(x/2)), a neutral apatite, and finnemanite, Pb(10)(As(3+)O(3))(6)Cl(2), a reduced apatite, were characterized using a combination of X-ray powder diffraction, neutron diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Both phases conform to hexagonal P6(3)/m symmetry; however, the temperature-driven transformation of clinomimetite to mimetite described earlier was not confirmed. The average mimetite structure is best described through the introduction of partially occupied oxygen sites. A better understanding of the mixed arsenic speciation in apatites can guide the formulation of waste form ceramics and improve models of long-term durability after landfill disposal.