Intercalated nanofilms with excellent intercalation effect, mechanical properties, anti-ultraviolet properties as well as barrier properties are obtained by introducing polyvinyl alcohol into chitosan/organic rectorite composite system. The polyvinyl alcohol (PVA)-chitosan (CS)/organic rectorite (OREC) series films were prepared by solution cape casting. The intercalation structure and dispersity of OREC in the matrix of composite films were analyzed by XRD and SEM. The mechanical and anti-ultraviolet properties as well as water vapor permeability were investigated. The results showed that the excellent intercalation structure of PVA-CS/OREC composite films could be obtained with low OREC and PVA content. The PVA10-CS/OREC2 composite film had the best intercalation structure when the mass fraction of OREC and PVA were 2% and 10% respectively. OREC had the best dispersity in the matrix of CS and PVA. Compared with the composite film (CS/OREC2) with 2% OREC but no PVA, the tensile strength and the elongation at break were 42.2% and 30% respectively higher and the water vapor transmission reduced by 10.2%. The tensile strength and elongation break of composite film by untraviolated radiation maintained at 82.5% and 68.2% respectively. In conclusion, PVA10-CS/OREC2 film can be used as medical film and also packing materials for food and pharmaceuticals, etc.