Cellulose is a linear polymer consisting of D-anhydroglucose units joined by β-1,4-glycosidic linkages. The densely packed cellulose molecular chain forms crystalline cellulose through strong hydrogen bonding. Owing to its chemical tunability and excellent mechanical resistance, nanocellulose is widely used in everyday life and the industrial sector. In this work, cellulose materials were nanoprocessed by mechanical ball-milling(1) in polar solvents(N,N-dimethylformamide or dimethyl sulfoxide) with esterification or(2) in hydrophobic agents(polydimethylsiloxane or polytetrafluoroethylene) with different molecular weights. Cellulose nanofibers and nanosheets with different hydrophilic and hydrophobic properties were obtained, and the mechanism of cellulose disintegration along a crystallographic plane induced by mechanical force and the polarity condition were discussed. This work affords a new way to manipulate the morphology and properties of nanocellulose. Cellulose is a linear polymer consisting of D-anhydroglucose units joined by β-1,4-glycosidic linkages. The densely packed cellulose molecular chain forms crystalline cellulose strong hydrogen bonding. Owing to its chemical tunability and excellent mechanical resistance, nanocellulose is widely used in everyday life and the industrial sector. In this work, cellulose materials were nanoprocessed by mechanical ball-milling (1) in polar solvents (N, N-dimethylformamide or dimethyl sulfoxide) with esterification or (2) in hydrophobic agents (polydimethylsiloxane or polytetrafluoroethylene ) with different molecular weights. Cellulose nanofibers and nanosheets with different hydrophilic and hydrophobic properties were obtained, and the mechanism of cellulose disintegration along a crystallographic plane induced by mechanical force and the polarity condition were discussed. This work affords a new way to manipulate the morphology and properties of nanocellulose.