Polybenzocoumarins, characterized by unique structural features, have emerged as a promising class of compounds with diverse applications. In the realm of fluorescence, these molecules exhibit notable properties attributed to their extended π‐conjugation, aromaticity, and potential for intramolecular charge transfer. Diverse synthetic methodologies, including green chemistry approaches and transition‐metal‐catalyzed reactions, are discussed. The review explores the impact of structural modifications on fluorescence behavior, providing insights for designing fluorescent probes. The versatility of polybenzocoumarins makes them promising in bioimaging, sensors, and optoelectronics. This concise overview serves as a valuable resource for researchers interested in the dynamic field of polybenzocoumarin chemistry.