A family of thermoresponsive poly(N-isopropylacrylamide) [PNIPAM]-grafted cellulose nanofibers (CNFs) was synthesized via a novel silver-promoted decarboxylative polymerization approach. This method relies on the oxidative decarboxylation of carboxylic acid groups to initiate free radicals on the surface of CNFs. The polymerization reaction employs relatively mild reaction conditions and can be performed in a one-step, one-pot fashion. This rapid reaction forms a C─C bond between CNF and PNIPAM, along with the formation of free polymer in solution. The degree of functionalization (DF) and the amount of PNIPAM grafted can be controlled by the Ag concentration in the reaction. Similar to native bulk PNIPAM, PNIPAM-grafted CNFs (PNIPAM-g-CNFs) show remarkable thermoresponsive properties, albeit exhibiting a slight hysteresis between the heating and cooling stages. Grafting PNIPAM from CNFs changes its cloud point from about 32 to 36 °C, influenced by the hydrophilic nature of CNFs. Unlike physical blending, covalently tethering PNIPAM transforms the originally inert CNFs into thermosensitive biomaterials. The Ag concentration used does not significantly change the cloud point of PNIPAM-g-CNFs, while the cloud point slightly decreases with fiber concentration. Rheological studies demonstrated the sol-gel transition of PNIPAM-g-CNFs and revealed that the storage modulus (G') above cloud point increases with the amount of PNIPAM grafted. The novel chemistry developed paves the way for the polymerization of any vinyl monomer from the surface of CNFs and carbohydrates. This study validates a novel approach to graft PNIPAM from CNFs for the synthesis of new thermoresponsive and transparent hydrogels for a wide range of applications.