Multifarious aromatic sulfone-decorated conjugated polymers (CPs) have recently been developed, in which the strong intramolecular interactions and extended conjugation facilitate charge transfer, enabling them to be employed in artificial photocatalysis with encouraging achievements. Nevertheless, there is a lack of systematic emphasis and summary of structural regulation about the reported sulfone-decorated CPs at a molecular level. Herein, the key advancements made in sulfone-decorated CPs, including covalent organic frameworks (COFs), conjugated microporous polymers (CMPs), and linear conjugated polymers (LCPs), are thoroughly disclosed. We first highlight various design strategies for the structural regulation that affects the charge separation and transfer dynamics and systematically discuss the relationship between their polymeric structures and photocatalytic performance. Recent advancements of sulfone-decorated CPs in various photocatalytic applications are also presented, covering the topics of photocatalytic H₂ evolution, organic transformation, oxidation of methane, reduction of uranium(VI), hydrogen peroxide (H₂O₂) generation, and NO removal. Finally, we envision the key challenges and prospects that need to be pursued with the aim of providing new insights and contributing to the game-changing innovations that could lead to the exploration of more attractive functionalities or applications in several emerging interdisciplinary research areas. It is expected that the systematic discussion in this review can serve as guidance and inspiration, delivering a comprehensive understanding of sulfone-decorated CPs and facilitating the development in the realm of CPs.