High costs and low performance have constrained the application of bio-based materials in food packaging. Herein, a series of ultra-thin poly(L-lactic acid-iconic acid N-diol) (P(LA-NI)) copolymer films were developed using a “one-step” polycondensation process with integrated toughness, barrier properties, gas selectivity, and quality control features. The massive branched structure and gg conformers in P(LA-NI) act as “internal chain expansion” and “internal plasticization”. Meanwhile, P(LA-NI) contains numerous polar groups and unique nanoscale microphase structures to realize excellent CO2, O2 barrier, CO2/O2 selectivity, anti-fogging, and UV shielding functions. The atmosphere within the package spontaneously achieves the desirable low O2 and high CO2 levels when packaging button mushrooms with high respiratory metabolism. Eventually, the shelf life of button mushrooms reached 24 days, >3-fold extended. This PLLA-based film meets “dual carbon” and “food safety” goals and has vast potential for fresh food preservation.