Graphene oxide (GO) nano-sheets were synthesized using a modified Hummers’ method from graphite powder. The Raman spectrum of GO displayed a D-band at 1359 cm^-1 and a G-band at 1594 cm^-1. The I_D/I_G value of GO was calculated to be 0.97, suggesting the formation of new sp² clusters upon reduction. A method was designed to investigate the assembly of the GO/montmorillonite (MMT) composite. After the addition of GO, the typical peaks of montmorillonite in FT-IR spectra shifted, indicating the assembly between GO and MMT. The D-band and G-band reduced sharply in the GO/MMT composite. More importantly, the D-band (1344 cm^-1) and G-band (1574 cm^-1) shifted significantly and the I_D/I_G value of the GO/MMT composite was calculated to be 1.13, showing a change in the GO structure. In the addition of 0.04 wt% GO to MMT, the value of interlayer space (d) was up to 13.0 ? measured by XRD due to the insertion of GO into MMT. The evident increases in contents of carbon atoms (26.59%) and nitrogen atoms (3.44%) indicate that GO was successfully combined with MMT. The nano-pores and clay sheets were not observed in the SEM image of GO/clay, but obvious wrinkles, while flexible sheets were observed in the typical scanning electron microscopy images of GO. This further proves that GO was combining with clay. The TEM image shows that the GO nano-sheets were tiled on the surface of MMT sheets. This observation suggests that a stable assembly structure was formed between GO sheets and MMT sheets. The change in particle size of MMT with the addition of GO shows that interaction occurred between GO sheets and MMT sheets, which was further confirmed by the results of zeta potential. Adsorption and insertion were the main mechanisms to assemble GO and MMT.