Cellulose nanofibers (CNFs) have been widely used as a renewable emulsifier to stabilize two immiscible liquids due to their intrinsic amphiphilicity and excellent emulsifying ability. However, it remains challenging to fully understand the effects of carboxylate group content and surface charge density on the emulsifying ability of CNFs and the stability of Pickering emulsion. Herein, carboxymethylated CNFs were extracted from bleached kraft pulp using etherification reaction and high-pressure homogenization, allowing for easy surface charge density and size adjustment by changing sodium chloroacetate content and homogenization cycles. The optimizing CNFs possessed a high Zeta potential (−71.2 mV) and a suitable carboxylate group content (1.81 mmol/g), which enabled CNFs to irreversibly adsorb at the hydrophobic paraffin wax (PW) droplet surface and form interfacial steric barriers, providing large electrostatic repulsion between the PW droplets against coalescence. Thus, the CNF-stabilized PW emulsions could be stored for more than 6 months. Moreover, the phase change enthalpy of the freeze-dried emulsion is as high as 193.7 J/g, which provides the emulsion to reversibly store and release heat. This work provides a comprehensive insight into the interfacial stability mechanism of CNFs as stabilizers and facilitates the potential application in thermal energy storage.