The structural location and effect of Sr partially substituting for Ca in chlorapatite, Cas(PO4)3C1, have been determined from crystal structure refinements with X-ray data from three synthetic single crystals having Sr/Ca ratios from 0.02 to ~1.0. The crystals are all hexagonal with space group P63/m. When present in small amounts, Sr substitutes only for Ca(2) on the mirror plane but at a slightly different position, as accommodates its larger ion radius. With 48% replacement of Ca by Sr, 68% of the Ca(2) sites and 19% of the Ca(I) sites (on the threefold axis) were filled by Sr. The CI atom shifts from 0,0,0.44 in chlorapatite to 0,0,½, its position in Srs(PO4)3CI, with increasing Sr content, dz/dA [where A is amount of Sr(2) present[ being greatest initially. Vegard's law is obeyed within 2a. The larger ion size and its preferential substitution on the border of the easy diffusion channel are the only observed features that could correlate with the known cariostatic effect of Sr in human tooth enamel or with the reported slight preferential loss of Sr that has replaced Ca in bone.