Kaolinite was intercalated with n-hexylamine, n-octadecylamine and n-docosanamine, using methanol-kaolinite as the precursor. The intercalation compound with n-docosanamine presented the largest basal spacing for a kaolinite derivative thus far reported (64.2 Å). Five grafted derivatives of kaolinite were directly intercalated with n-hexyl- and n-octadecylamine. During intercalation, the grafted molecules rearrange from parallel to perpendicular orientation to the kaolinite surface, in order to maximize the interaction with the amine and minimize the interlayer expansion needed. The octadecylamine intercalation compounds were delaminated in toluene, accompanied by the deintercalation of the amine molecules. Thin kaolinite particles rolled into a halloysite-like morphology, but forming much smaller tubes, some of which possibly consist of single kaolinite layers. The delamination was more efficient with the grafted kaolinites than with raw kaolinite.