Doping silicon with arsenic by ion implantation above the solid solubility level leads to As clusters and/or precipitates in the form of monoclinic SiAs causing electrical deactivation of the dopant. Information on the local structure around the As atom, and the As concentration depth profiles is important for the implantation and annealing process in order to reduce the precipitated As and maximize the electrically activated As. In this study, we determined the local As structure and the precipitated versus substituted As for As implants in CZ (001) Si wafers, with implant energies between 20 keV and 100 keV, and implant doses ranging from 1 × 1015/cm2 to 1 × 1018/cm2. The samples were subjected to different thermal annealing conditions. We used secondary ion mass spectrometry (SIMS) and UT- MARLOWE simulations to determine the region where the As-concentration is above the solid solubility level. By x-ray absorption fine structure spectroscopy (XAFS), we probed the structure of the local environment around As. XAFS being capable of probing the short-range order in crystalline and amorphous materials provides information on the number, distance and chemical identity of the neighbors of the main absorbing atom. Using Fourier analysis, the coordination numbers (N) and the nearest-neighbor distances (R) to As atoms in the first shell were extracted from the XAFS data. When As precipitates as monoclinic SiAs, the nearest-neighbor distances and coordination numbers are ∼2.37 Å and ∼3, as opposed to ∼2.40 Å and ∼4 when As is substitutional. Based on this information, the critical implant dose where the precipitation/clustering of As starts, and the ratio of the substitutional versus cluster/precipitate form As in the samples were determined.