Plasticizers are vital additives that modify the functional performance of edible films and coatings by improving flexibility, reducing brittleness, and enhancing processing characteristics. Their incorporation into starch-based biopolymer matrixes alters the structural arrangement by disrupting strong intermolecular hydrogen bonds and increasing polymer chain mobility. This restructuring enables improved film-forming ability and mechanical compliance, making the films more suitable for packaging applications. This chapter explores the role of plasticizers in modifying the functional properties of edible films and coatings. By analyzing the effects of different plasticizers on key attributes such as water absorption, solubility, oxygen permeability, water vapor transmission rate (WVTR), thermal behavior, and mechanical properties, we aim to provide a comprehensive understanding of their impact.