Polyhydroxyalkanoates (PHAs) are biodegradable biopolymers produced by a diverse range of microorganisms as intracellular carbon and energy storage compounds. Due to their potential to replace petroleum-based plastics, PHAs have attracted significant industrial and environmental interest. However, the commercialization of PHAs is challenged by high production costs, low yields, and process inefficiencies. This chapter explores the biosynthesis and metabolic pathways underpinning PHA production, alongside microbial mechanisms involved in their degradation. Special emphasis is given to the emerging concept of elicitation strategies in microbial systems—a promising approach to enhance PHA yield and productivity. By understanding how biotic and abiotic elicitors modulate microbial metabolism, researchers can develop innovative bioprocessing strategies to overcome current production barriers. This chapter aims to provide a comprehensive insight into the integration of elicitation in microbial PHA production and its future prospects in sustainable biomanufacturing.