The twice intercalation method to prepare organic-intercalated montmorillonites with dimethylacetamide (DMC) and cetyltrimethylammonium bromide(CTAB) as intercalating agents was introduced and compared with the once intercalation method. It showed that the interlayer distance of montmorillonite enlarged from about 1 nm to 3 nm or so after twice intercalation , which made the organic molecules easily to enter and form new montmorillonite/polymer composite.