A versatile approach was developed for the preparation of cross-linked attapulgite (ATP)-nitrile butadiene rubber (NBR) nanocomposites or NBR grafted ATP nanorods, by facilely adjusting the feeding ratio between the butadiene-based rubbers and the thiol-modified attapulgite (ATP-SH) nanorods in a facile thermal-triggered thiol–ene interfacial click reaction. The modified products with different feeding ratios between the ATP-SH and NBR were characterized with FT-IR, TGA, and TEM techniques. The results indicated that the cross-linked ATP-NBR nanocomposites could be produced via the thiol–ene interfacial click reaction with excess NBR, while the NBR grafted ATP nanorods could be synthesized via the reaction with excess ATP-SH nanorods. Based on the results, a possible mechanism and potential applications were proposed.