Agro-wastes are derived from diverse sources including grape pomace, tomato pomace, pineapple, orange, and lemon peels, sugarcane bagasse, rice husks, wheat straw, and palm oil fibers, among other affordable and commonly available materials. The carbon-rich precursors are used in the production bio-based polymers through microbial, biopolymer blending, and chemical methods. The Food and Agriculture Organization (FAO) estimates that 20–30% of fruits and vegetables are discarded as waste during post-harvest handling. The development of bio-based polymers is essential, considering the scale of global environmental pollution that is directly linked to the production of synthetic plastics such as polypropylene (PP) and polyethylene (PET). Globally, 400 million tons of synthetic plastics are produced each year, and less than 9% are recycled. The optical, mechanical, and chemical properties such as ultraviolet (UV) absorbance, tensile strength, and water permeability are influenced by the synthetic route. The production of bio-based polymers from renewable sources and microbial synthesis are scalable, facile, and pose a minimal impact on the environment compared to chemical synthesis methods that rely on alkali and acid treatment or co-polymer blending. Despite the development of advanced synthetic methods and the application of biofilms in smart/intelligent food packaging, construction, exclusion nets, and medicine, commercial production is limited by cost, the economics of production, useful life, and biodegradation concerns, and the availability of adequate agro-wastes. New and cost-effective production techniques are critical to facilitate the commercial production of bio-based polymers and the replacement of synthetic polymers.