We previously studied a suitably 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) that can be further functionalized with initiating sites and overcame the obstacle of performing atom transfer radical polymerization (ATRP) in the presence of neutral carboxylic acid sodium salt groups [1]. Herein, characterization of the modified TOCNs and of the products from surface-initiated (SI) ATRP of the (nano)celluloses with styrene (St) was performed using nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and contact angle (CA) measurements. From the analysis of (1)H NMR, a high purity of sacrificial initiator (i.e., 2-hydroxyethyl 2-bromoisobutyrate (HEBiB)) was confirmed. HEBiB was utilized to trace the SI ATRP with the generated free PSt. Gradually molecular weight evaluations were revealed from GPC analysis (ca. M n=21,000 and Đ=1.10) using different TOCNs, implying the insignificant contribution to the kinetics from the grafted initiating sites. The TOCN-g-PSts were further characterized by contact angles and displayed an obvious reversibility between hydrophilicity and hydrophobicity in tens of minutes. These results illustrated a simple and facile approach for controlling the graft length and composition of TOCNs through SI ATRP.