Persistent organic pollutants (POPs) generated during coal combustion have become a global focus of environmental governance because of their environmental persistence, bioaccumulation potential, and toxic effects. This study systematically reviews the formation mechanisms, emission characteristics, control technologies, and health risks of coal-derived POPs, such as polycyclic aromatic hydrocarbons (PAHs), halogenated PAHs (HPAHs), polychlorinated biphenyls (PCBs), and dioxins and furans. This study shows that POP formation is regulated by chemical kinetic pathways (precursor generation, halogenation, and surface-catalyzed synthesis) and the coupled effects of combustion conditions, coal properties, and fly ash catalysis. Their emission intensity is determined by the synergistic effects of combustion parameters, coal quality, and end-of-pipe control technologies. Remarkable heterogeneity exists in POP emissions from different combustion devices: PAHs are predominantly enriched in fine particles (particulate matter 2.5, PM2.5), whereas emissions of HPAHs and PCBs are considerably influenced by coal chlorine content and combustion technologies. Current precombustion treatment, in-combustion control, and postcombustion technologies partially reduced POPs; however, breakthroughs are needed for identifying emerging pollutants, analyzing cross-media migration mechanisms, and improving global governance frameworks. Human exposure to POPs through inhalation and dietary intake may cause respiratory, immune, and reproductive system diseases, with health risks exceeding safety thresholds in some regions. Future research should focus on the characteristics of emerging pollutants, optimizing synergistic emission reduction technology systems, and improving multimedia risk assessment frameworks.