Modified kaolinites possess excellent adsorption properties and, therefore, are regarded widely as potential catalytic components. The use of modified kaolinites as a catalytic component for Fischer–Tropsch synthesis (FTS) has remained unexplored, however. In the current study, delaminated and pit-rich nano-kaolinite was prepared via acid treatment of N-methylformamide (NMF)-intercalated kaolinite (intercalation-etching strategy), and was used as a support to prepare a cobalt-based FTS catalyst (denoted as 15%-Co-HNKln). Compared with other FTS catalysts, the supports for which were raw kaolinite or directly acid-treated kaolinite, the 15%-Co-HNKln showed several advantages such as large specific surface area, dispersed Co particles with small particle size, more new active sites, and significant surface acidity. Given the aforementioned advantages, the 15%-Co-HNKln catalyst demonstrated very good FTS performance. Compared with that of the raw kaolinite-supported FTS catalyst, the CO conversion rate and C5–C12 hydrocarbon selectivity of 15%-Co-HNKln increased by 20% and 15%, respectively.