The integration of inorganic materials with biological machinery to convert plastics into fuels offers a promising strategy to alleviate environmental pollution and energy crisis. Herein, we develop a type of hybrid living material via biomineralization of CdS onto Shewanella oneidensis‐based biofilm, which is capable of sustainable hydrogen production from poly(lactic acid) (PLA) wastes under daylight. We reveal that the formed biofilm microstructure provides an independent anaerobic microenvironment that simultaneously supports cellular viability, maintains hydrogenase activity, and preserves the functional stability of CdS, giving rise to the efficient plastic‐to‐hydrogen conversion efficiency as high as 3751 μmol H2 g‐1 PLA. Besides, by genetically engineering transmembrane pili conduit and incorporating conductive nanomaterials to strengthen the electron transfer across cellular interface and biofilm matrices, we show that the conversion efficiency is further enhanced to 5862 μmol H2 g‐1 PLA. Significantly, we exhibit that a long‐term sustainable plastic‐to‐hydrogen conversion of 63 d could be achieved by periodically replenishing PLA wastes. Overall, by the synergistic integration of biotic‐abiotic characteristics the developed biofilm‐based biomineralized hybrid living material is anticipated to provide a new platform toward the efficient conversion of plastic wastes into valuable fuels, and bridge the gap between environmental contamination and green energy production.