A sustainable approach to microbial polyhydroxyalkanoate (PHA) production involves utilizing waste as a substrate, which can include toxic pollutants like phenol as a carbon feedstock. Phenol-contaminated effluents offer cost-effective and readily available resources for PHA production, while simultaneously addressing phenol contamination issues. Understanding the metabolic conversion of phenol to PHA is crucial to enhance its efficiency, especially considering phenol's toxicity to microbial cells and the substrate-dependent nature of microbial PHA production. In this review, the mechanisms of phenol biodegradation and PHA biosynthesis are first independently elucidated to comprehend the role of bacteria in these processes. Phenol can be metabolized aerobically via various pathways, including catechol