Cellulose nanofibrils (CNFs) are a natural resource with a sustainable supply and can be used in various industrial fields, such as paper, plastics, and medical supplies. However, CNFs have a low resistance to moisture. To solve this problem, hydrophobicity of CNF should be enhanced. In the papermaking process, a rosin sizing agent is used to induce hydrophobicity. This process uses alum that can be replaced with cationic CNFs. Therefore, the quaternary amination pretreatment was performed on CNFs to obtain cationic CNFs. Then, these cationic CNFs were stirred with a rosin sizing agent to prepare a film. The resulting film exhibited a high contact angle and strong hydrophobicity.