Reversible deactivation radical polymerization (RDRP) is a set of powerful and versatile methods for the synthesis of well-defined polymers. Over the past two decades, the engagement of biocatalysts, namely, enzymes and bacteria, has granted distinctive features to RDRP and propelled RDRP toward a more sustainable future. In this Perspective, we highlight the green conditions, oxygen tolerance, versatile function, and the ability to access difficult polymers in RDRP conducted by biocatalysis (bio-RDRP), discuss major considerations when conducting bio-RDRP, and point out the drawbacks and bottlenecks that limit its further development. The future of bio-RDRP may benefit from expanding the biocatalyst library, improving the redox potential of bacteria, enhancing the biocatalyst robustness, and in-depth mechanistic studies.