Bio-based superhydrophobic coatings have attracted great attention owing to their environmental friendliness and potential applications. Among them, cellulose ester-based coatings show excellent superhydrophobicity. Even so, their rational design and performance modulation have been rarely concerned, which is of great importance to their practical applications. Herein, we adjusted the superhydrophobicity and self-binding strength of alpha-cellulose 10-undecenoyl ester (CUE) coatings (used as a model) by changing the degree of substitution (DS) value. The DS-induced particle size of the CUE played a key role in the cluster formation for the superhydrophobicity and the generation of contact area for the binding force. The CUE size displayed a normal distribution with the increase in DS value, and a low coating amount as well as a high contact area could be realized from a large particle size. The optimum DS value of the CUE coating was 0.44-0.94. This research may provide a new perspective for the design of stable bio-based superhydrophobic coatings.