The global increase in population, urbanization, and industrialization has led to a growing demand for energy, contributing to increased pollution levels, particularly from rubber and plastic waste. Despite being essential in industrial processes, millions of tons of waste are generated annually, posing a serious environmental threat. Currently, of the 400 million tons of plastic produced each year, it is estimated that less than 10% of it is properly recycled. Biological degradation methods, using microorganisms to detoxify contaminated environments, are currently gaining prominence. However, challenges such as polymer complexity and enzymatic efficiency must be addressed. This review aims to address the primary challenges in enzymatic fragmentation of two model polymeric materials: rubber and polyethylene terephthalate (PET). For this, the role of crucial enzymes, including rubber oxygenases such as latex clearing protein (Lcp), and hydrolases such as PETase was identified, emphasizing the importance of mass transfer limitations, product inhibition, and the presence of additives for an efficient conversion bioprocess. The utilization of enzymatic reactors for simultaneous catalysis and product separation is considered innovative and promising for enhancing the efficiency of the degradation process, enabling a more effective polymer fragmentation through enzyme action. An integrated approach holds the potential to be a more sustainable solution to address environmental challenges associated with plastic and rubber pollution.