Polyfluoroaryl compounds belong to privileged moieties and engender distinct properties in many pharmaceuticals, agrochemicals, and materials. Over the past decade, considerable seminal reports and reviews have merely paid close attention to fluoroalkylation chemistry, such as trifluoromethylation, difluoroalkylation, perfluoroalkylation, trifluoromethylthiolation or trifluoromethoxylation. Polyfluoroarylation has inevitably lagged somewhat behind its fluoroalkylation counterparts, emanating from a lack of awareness and understanding of the synthetic significance. Together with the renaissance of photochemistry, the photocatalytic polyfluoroarylation using polyfluoroarenes as an inexpensive and easy-available radical precursor has emerged as a topical interest and vibrant area of chemical research. In this review, we have endeavored to present the state-of-the-art in photocatalytic polyfluoroarylation since 2014, and the discussions cover the basic concept, reaction design, mechanistic insight, and research prospects, which are organized by the reaction types. We hope this review will provide a comprehensive overview of this topic and stimulate significant research interest.