•PFOTES was used to enhanced the tribo-polarity and hydrophobicity of CNF-based TENG.•PFOTES-CNF-based TENG exhibit enhanced triboelectric performance.•The Isc reached 9.3 μA, which is about twice that of a pure CNF-based TENG.•The PFOTES-CNF-based TENG retains 70% of the initial output at 70% ambient humidity. Cellulose is the most abundant natural polymer on earth. Because it is renewable, biodegradable, and biocompatible, it offers distinct advantages as a starting material for bio-based triboelectric nanogenerator (bio-TENG). However, weak polarity, poor hydrophobicity, and insufficient functionalization on the natural cellulose surface severely limit the development of high-performance cellulose-based TENGs. In this work, chemical functionalization is employed to control the surface polarizability and hydrophobicity of cellulose nanofibrils (CNFs). Functional groups on the CNF surface are modified with triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (PFOTES) in a straightforward and facile process. Fluorine-bearing silane chains are grafted to the surface of CNFs, which increases their triboelectric charge density and improves their hydrophobicity. Experimental results demonstrate that the surface polarity of CNFs is greatly improved after PFOTES modification. The PFOTES-CNF-based TENG exhibits good resistance to humidity and long-term cycle stability, and it retains 70% of the initial output performance at 70% ambient humidity. The short-circuit current of the PFOTES-CNF-based TENG reached 9.3 μA, which is about twice that of CNF-based TENG prior to modification. These results clearly indicate that PFOTES can be used to control CNF surface polarizability and hydrophobicity, advancing the search for durable, high-performance, degradable bio-TENGs.