Efficient and effective use of biopolymers, such as starch, has increasingly prompted interest due to the current environmental challenges. However, starch-based composites still show poor ductility along with water and oxygen permeability, which may not meet the requirements for food packaging standards. In this study, modified starch (m-St), isolated from the avocado seed and synthesized with tert-butyl acetoacetate (t-BAA), was embedded into polylactic acid (PLA) to design new eco-friendly composites. The developed biocomposites were found to exhibit high performance with outstanding mechanical properties in conjunction with remarkable light, water vapor, and oxygen blocking features for food packaging applications. PLA/m-St(1:6) 20 wt% composites showed a dramatic increase in elongation at break (EB%) from 3.35 to 27.80 % (about 730 % enhancement) and exhibited remarkable UV-blocking performance from 16.21 to 83.86 % for UVB, relative to pure PLA. Equally importantly, these biocomposites revealed significant improvement in oxygen and water vapor barrier performance by reducing their values from 1331 to 32.9 cc m−2 day−1 (indicating a remarkable reduction of 97.53 %) and 61.9 to 28 g m−2 day−1, respectively. This study can show the great potential of extracting starch from biowaste resources and transforming it into sustainable bio-based composites as a promising solution for food packaging applications.