Abstract: Cellulose, the most abundant natural polymer on Earth, displays notable potential. However, its low solubility in conventional solvents and poor melt processability restrict its broader application. To overcome these limitations, chemical modification, particularly esterification, has proven to be an effective strategy to enhance cellulose processability. As the earliest cellulose derivatives, cellulose esters have found widely applications in textiles, pharmaceuticals, coatings and film science. Beyond traditional uses, cellulose esters exhibit chiral nematic liquid crystal behavior, opening new avenues in functional materials. This review systematically examines the inherent chirality of cellulose across multiple structural scales, summarizes key esterification modification strategies, and analyzes the chiral nematic liquid crystal behavior of cellulose esters and their applications in chiral materials. Furthermore, we discuss current challenges in cellulose ester fabrication and highlight promising future directions. By combining theoretical and practical insights, this work aims to provide a comprehensive understanding of cellulose esters’ physicochemical properties and their applications in functional materials.