The short-term shelf life of straw mushrooms (Volvariella volvacea) is a major challenge, hampering their wide distribution. Thus, the aim of this work was to develop a novel active packaging composed of essential oils (EOs), particularly clove oil (CO) and peppermint oil (PO), to reduce autolysis of straw mushrooms. The morphological characterizations, mechanical properties, barrier properties, and antioxidant activities of the films were characterized. The suppressive effects of the EOs on straw mushroom autolysis were estimated during storage at 16 ± 1 °C for 96 h. The results indicated that the addition of EOs weakened the mechanical and barrier properties of the films. The radical-scavenging activities of polylactic acid/poly(butylene adipate-co-terephthalate)/thermoplastic starch-peppermint oil (PLA/PBAT/TPS-PO) and polylactic acid/poly(butylene adipate-co-terephthalate)/thermoplastic starch-clove oil (PLA/PBAT/TPS-CO) films for 2,2-diphenyl-1-picrylhydrazyl were 56.0% and 91.3%, respectively. However, the PLA/PBAT/TPS-PO film was more effective in reducing polyphenol oxidase activity and maintaining the total phenol content of straw mushrooms, demonstrating better antioxidative activity. Mushrooms packaged with the PLA/PBAT/TPS-PO film exhibited the lowest autolysis rate (42.29%, p < 0.05) after 96 h of storage. Thus, PO is a good preservative agent for straw mushroom.