Carboxylate (TCNF) and sulfonated (SCNC) cellulose nanofibers were synthesized and used as adsorbents for metallic cations in aqueous solutions: Na⁺ and Hg²⁺ (SCNC); Mg²⁺ and Hg²⁺ (TCNF). ICP-OES analysis of the liquid phase revealed metal removal efficiencies at room temperature of 89.3% (Hg²⁺) and 100% (Mg²⁺) for TCNF, 35.2% (Hg²⁺) and 63.3% (Na⁺) for SCNC after 3 h of contact. Interestingly, the nanofibers exhibited a distinct thermal degradation profile (characterized by two main events) compared to that of cellulose, suggesting that their nanostructured morphology and surface functionalization may enhance thermal instability. Additionally, the presence of metals at its surface notably altered the thermal degradation kinetics, as observed for mercury and magnesium in TCNF. Finally, the results for SCNC strongly suggest that the mechanism for thermal degradation can also change, as observed for mercury and sodium, expressed through the appearance of a new DTG peak located around 300 °C.