Quasicrystals of synthetic fluoromagnesian smectite (FMS) in dodecyltrimethylammonium chloride (DTAC) solutions were investigated as a function of the DTAC concentration by wet type X-ray diffraction (XRD) ζ potential measurements, and dispersion and coagulation (DC) tests. The FMS had an electronegative potential and it was dispersed randomly in an aqueous suspension without DTAC. When the DTAC concentration was 0.002 mol/dm3, FMS tactoids started to develop a structure in which the layer thickness was 1.85 nm. At the isoelectric point, the DTAC concentration was 0.012 mol/dm3 and the FMS tactoid formed a regular stacked structure with a 2.25 nm layer thickness. As the ζ potential of FMS changed from negative to positive, the DC test and XRD measurement showed that the FMS association gradually changed from coagulation to dispersion, which indicates that the formation of the bilayer of surfactants on the surface of FMS produces a repulsion between DTA+ adsorbed on the silicate layer of the FMS surfaces. When the equilibrium concentration of DTAC in solution exceeded the critical micelle concentration (CMC), the ζ potential of FMS became greater than the previous values. The XRD analysis of this suspension showed that there were two kinds of rational FMS stackings; one has a layer thickness of 3.20 nm, and the other has a layer thickness of 5.45 nm due to an interstratified structure composed of 3.20 and 2.25 nm layers. The interstratified structure was confirmed by the calculated XRD profiles.