A series of arsenate substituted chlorapatite was directly prepared through aqueous precipitation method. Characterization studies from elemental analysis, XRD, FT-IR spectra and SEM confirmed the forming of the arsenate/phosphate chlorapatite solid solutions. The XRD analysis indicated the typical solid solution phase of the apatite-type structure. In FT-IR spectra, the area of the phosphate peak was gradually suppressed and the arsenate peak increased as the proportion of the arsenate increased. The solids with As/(As+P) molar ratio of 0.49~1.0 were needle-like crystals; those with As/(As+P) molar ratio <0.19 were large tabular.