In this study, X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR) together with Scanning probe microscopy (SPM) were used to characterize the structure and morphology of the complexes, where the hydrobiotites (Xinjiang) were modified by single-chain surfactants octyltrimethylammonium bromide (OTMA) and octadecyltrimethylammonium bromide (ODTMA).XRD patterns showed that the structure of complexes was significantly influenced by the surfactant concentration and the alkyl chain length, because obvious changes took place in the basal spacing.Furthermore, according to the XRD results, several arrangements of surfactant molecules within the hydrobiotite interlayer space were deduced.The FTIR spectrum indicated that the surfactant contents in complexes dramatically increased with the alkyl chain length.The SPM micrographs demonstrated that the surfaces of complexes prepared at lower surfactant concentration were relatively flat compared with that prepared at higher concentration, while those with higher surfactant concentration had much steeper surface due to the alkyl chain length.It was concluded that structure and morphology of surfactant/hydrobiotite complexes depend not only on the surfactant concentration, but also strongly on the surfactant species.