Advancements in directed evolution and genome sequencing have led to the discovery and evolution of enzymes with new and improved catalytic properties. The pharmaceutical industry has greatly benefited from this, evidenced by the number of publications and manufacturing processes reported in the last decade. However, biocatalysts are rarely reported in the polymer industry which has prompted the writing of this review to highlight enzymatic processes towards the production of structurally diverse monomers. These highlights detail the process development, evolution and novel use of enzymes in polymer synthesis for medical, packaging and coating applications. The review features the use of four enzyme classes, oxidoreductases, transferases, hydrolases and lyases in the synthesis of high-value monomers found in commercial and next-generation biodegradable polymers.