Synthetic vinyl polymers have long been recognized for their potential to be utilized in drug delivery, tissue engineering, and other biomedical applications. The synthetic control that chemists have over their structure and properties is unmatched, allowing vinyl polymer-based materials to be precisely engineered for a range of therapeutic applications. Yet, their lack of biodegradability compromises the biocompatibility of vinyl polymers and has held back their translation into clinically used treatments for disease thus far. In recent years, radical ring-opening polymerization (rROP) has emerged as a promising strategy to render synthetic vinyl polymers biodegradable and bioresorbable. While rROP has long been touted as a strategy for preparing biodegradable vinyl polymers for biomedical applications, the translation of rROP into clinically approved treatments for disease has not yet been realized. This review highlights the opportunities for leveraging rROP to render vinyl polymers biodegradable and unlock their potential for use in biomedical applications.