The local structural environment of Co sorbed on hectorite (a magnesian smectite) has been investigated by polarized EXAFS (P-EXAFS) spectroscopy on a self-supporting film of Co-sorbed hectorite, This sorption sample was prepared by contacting Co and hectorite at pH 6.5 and at high ionic strength (0.3 M NaNO3) to favor pH-dependent sorption reaction over cation exchange, A self-supporting film was elaborated after 120 h of reacting time, when apparent quasi-equilibrium conditions were attained. The half-width at half maximum of the orientation distribution of c* axis of individual clap platelets off the film normal was determined by quantitative texture analysis, and found to be equal to 18.9 degrees, Co K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 0 degrees, 35 degrees, 50 degrees, and 60 degrees; the 90 degrees spectrum was obtained by extrapolation. Spectral analysis led to the identification of the two nearest cationic subshells containing 1.6 +/- 0.4 Mg at 3.03 Angstrom and 2.2 +/- 0.5 Si at 3.27 Angstrom. These distances are respectively characteristic of edge-sharing Linkages between Mg and Co octahedra and of corner-sharing linkages between Co octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Co-Mg and Co-Si contributions indicates that Co-Mg pairs are oriented parallel to the film plane, whereas Co-Si pairs are not, These results are interpreted by the formation of Co inner-sphere mononuclear surface complexes located at the edges of hectorite platelets, in the continuity of the (Mg, Li) octahedral sheet.