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Polycyclic aromatic hydrocarbons (PAHs), regarded as a class of hazardous pollutants due to their persistence and toxicity, are ubiquitous in the environment. Much research has been conducted on aerobic microbial degradation of some PAHs and determination of the degradation pathways for which synthesis of metabolic intermediates and metabolites is required. This mini-review briefly summarizes synthesis of commercially unavailable metabolites of phenanthrene, anthracene, pyrene, fluoranthene, and benzo[a]pyrene.