This study explores the development of environmentally sustainable, high‐quality packaging materials by incorporating poly(hydroxybutyrate) (PHB) with different polymers. To accomplish this objective, pure PHB was blended with poly(ethylene glycol) (PEG) in a precise 9:1 ratio. Subsequently, this blend was further combined with 50 wt% of various polymers, namely, polycaprolactone, poly(vinylacetate), and polylactic acid (PLA), using a solvent‐casting method. Further, the research investigates the multifaceted properties of these materials, including their thermal characteristics, morphological structures, mechanical strengths, barrier properties, and degradation behaviors. Among these blends, the film consisting of PHB, PEG, and PLA (PHB/PEG/PLA) emerged as a standout performer, displaying exceptional attributes. Notably, the PHB/PEG/PLA composite film exhibited remarkable thermal stability, boasting a high tensile strength of 26.6 MPa. Additionally, it demonstrated an outstanding ability to serve as a barrier against water vapors. These findings imply that the PHB/PEG/PLA composite film holds significant potential for a wide range of applications, particularly in the field of packaging and beyond.