Atom transfer radical polymerization (ATRP) is a leading method for creating polymers with precise control over molecular weight, yet its reliance on metal catalysts limits its application in metal-sensitive and environmental contexts. Addressing these limitations, we have developed a recyclable, biocompatible, robust, and tunable ATRP catalyst composed of a protein-polymer-copper conjugate, synthesized by polymerizing an L-proline-based monomer onto bovine serum albumin and complexing with Cu(II). The use of this conjugate catalyst maintains ATRP's precision while ensuring biocompatibility with bothEscherichia coli and HEK 293 cells, and its high molecular weight allows for easy recycling through dialysis. Therefore, our efforts extend ATRP's applicability across diverse fields, including biotechnology and green chemistry, marking a significant advance toward environmentally friendly and safe polymerization technologies.