Bulk mineralogical and chemical properties of a weathering profile derived from serpentinite were studied using classical pedological methods (Munsell soil colors, particle-size distribution, density, cation exchange capacity, exchangeable bases, among others) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) results. Bulk clay fractions were characterized using X-ray diffraction, thermal analysis, electron microprobe, Mössbauer and infrared spectroscopies. Bulk geochemical mass-balance calculated from ICP-AES results shows leaching of both Mg and Si which reflects the early weathering of serpentine minerals. As a consequence, newly formed clay minerals are enriched with the least mobile elements, i.e. Fe and Al, producing dioctahedral smectites. These dioctahedral smectites are complex, heterogeneous and consist mainly of two populations. One population is an Fe-rich montmorillonite with little or no tetrahedral charge and Fe3+ as the dominant octahedral cation whereas the second population exhibits tetrahedral charge. Both populations occur as interstratified layers in the lower horizon of the weathering profile but show increasing segregation into well-defined end-members towards the surface horizons. Considering total Al and Fe contents, these clays differentiate into two chemical composition domains, Fe-rich clays in the lower profile and Al-rich clays towards the surface horizons.