AbstractBiotechnological recycling offers a promising solution to address the environmental concerns associated with waste plastics, particularly polyethylene terephthalate (PET), widely utilized in packaging materials and textiles. To advance the development of a bio‐based circular plastic economy, innovative upcycling strategies capable of generating higher‐value products are needed. In this study, we enhanced the enzymatic depolymerization of waste PET by incorporating highly concentrated calcium ions (up to 1 m) to the hydrolytic reaction catalyzed by the best currently known enzyme LCC^ICCG. The presence of calcium ions not only improved the thermal stability and activity of the biocatalyst but also significantly reduced the consumption of base required to maintain optimal pH levels. Employing optimized conditions at 80 °C for 12 h, we successfully converted ≈84 % of the waste PET (200 g L⁻¹) into solid hydrated calcium terephthalate (CaTP ⋅ 3H₂O) as the primary product instead of soluble terephthalate salt. CaTP ⋅ 3H₂O was easily purified and employed as a raw material for battery electrode production, exhibiting an initial reversible specific capacity of 164.2 mAh g⁻¹. Through techno‐economic analysis, we conclusively demonstrated that the one‐pot biocatalysis‐based synthesis of CaTP is a superior PET upcycling strategy than the secondary synthesis method employing recycled terephthalic acid.