This article presents the inaugural intercalation study of a layered metal sulfonate network, Silver triflate forms intercalation complexes with straight chain primary alcohols from ethanol (C2H5OH) to eicosanol (C20H41OH)). Single-crystal data for the EtOH adduct, 1, are presented which show that the intercalation is coordinative to Ag. In contrast to many other layered hosts, no preheating of Ag triflate is required to liberate a coordination site for intercalation to take place, owing to the ability of the triflate ion to reorient. Crystal structure parameters for 1: C4H6F6S2O7Ag2, a = 5.345(7) Angstrom, b = 11.310(2) Angstrom, c = 12.004(2) Angstrom, alpha = 116.87(1)degrees, beta = 90.46(1)degrees, gamma = 99.59(1)degrees, triclinic, space group P1, Z = 2. Intercalate 1 presents the triflate ion in an unprecedented mu(5)-coordination mode. PXRD data on the family of complexes show that the intercalation is topotactic, as verified by the linear increase in d-spacing and calculated c-axis lengths for the intercalates, with increasing chain length. The data also show that the alcohol intercalates adopt an interdigitated rather than bilayer arrangement.