The morphology of PVA/Na-MMT composite under different freezing technology conditions was studied. Inlfuence of PVA content and frozen conditions on microstructure and formation mechanism of PVA/Na-MMT composite materials were analyzed using scanning electron microscopy(SEM). The experiment results show that the structure of freeze-dried PVA/Na-MMT composite is influenced by both frozen technology and PVA dosage. PVA/Na-MMT composite frozen in Low-temperature refrigerator presented honeycomb-like structure when PVA dosage was 1%, and when the dosage of PVA was 2%, 3%, 4% respectively, the composite exposed wrinkle superposition structure. In liquid nitrogen frozen, Fiber-like structure of PVA/Na-MMT composite was obtained when the PVA content more than 3%.