The crystal structure of stephanite from the type locality, Freiberg District, Saxony, Germany, was refined in the space group Cmc2(1), up to a final R index of 0.0427. Unit-cell parameters are: a 7.8329(6) angstrom, b 1 2.458(1) angstrom, c 8.5272(7) angstrom, V 832.1(1) angstrom(3); Z = 4. The previously reported structural model is confirmed, hilt a higher-precision refinement was achieved herein by the introduction of third-order non-harmonic Gram-Charlier tensors for one Ag atom. In the structure of stephanite, Sb forms isolated SbS3 pyramids, which typically occur in sulphosalts, and Ag occupies sites with coordination ranging from triangular to almost tetrahedral. Both the Sb-S and Ag-S bond distances closely match the values commonly observed in the structures of other Ag sulphosalts and sulphides. The use of non-harmonic parameters for Ag allowed a better description of the electron density related to Ag, which is usually difficult to refine in good ionic conductors. A careful analysis of the energy barriers between the Ag sites defines preferred ion-diffusion pathways within the crystal structure of stephanite. The diffusion of Ag ions occurs preferentially along the sites Ag1 and Ag2, giving rise to two-dimensional nets of Ag atoms in which the ion conduction probably takes place.