As-bearing travertine rocks from Tuscany (Italy), where previous studies suggested the existence of a CO32− ⇔ AsO33− substitution in the calcite lattice, were investigated with X-ray Absorption Spectroscopy (XAS) at the As K-edge (11,867 eV). In two of the studied samples, XANES indicates that As is in the 5+ oxidation state only, and EXAFS analysis reveals a local environment typical of arsenate species. For these samples, the lack of detectable second shell signals suggests a poorly ordered environment, possibly corresponding to an adsorption onto oxide and/or silicate phases. On the other hand, in the third sample XANES reveals a mixed As oxidation state (III and V). This sample also presents evident next nearest neighbor coordination shells, attributed to As-Ca and As-As contributions. The occurrence of next neighbor shells is evidence that part of As is incorporated in an ordered lattice. Furthermore, the local structure revealed by EXAFS is compatible with As incorporation in the calcite phase, as further supported by DFT simulations. The observation of next neighbors shells only in the As(III)-rich sample suggests the substitution of the arsenite group in place of the carbonate one (CO32− ⇔ AsO33−). The conclusion of this work is that uptake of As by calcite is in general less favored than adsorption onto iron oxhydroxides, but could become environmentally important wherever the latter phenomenon is hindered.