Catalysts play a key role in the production of cellulose acetate (CA). In this study, CA derived from bamboo cellulose (BC) was synthesized in a solution mixture of acetic acid and acetic anhydride that contains catalysts. The catalytic activities of three catalysts (i.e., sulfuric, methyl benzene sulfonic, and dodecyl benzene sulfonic acids) were investigated in terms of kinetics of acetylation, which was established according to the first-order reaction mechanism. Based on this, cellulose-based nanofibers were further prepared from the acetylated BC solution using an electrospinning technique. Results in this study may be useful for the preparation and application of nanomaterials derived from natural polymeric materials.