Visible light-regulated metal-free polymerizations have attracted considerable attention for macromolecular syntheses in recent years. However, few organic photocatalysts show high efficiency and strict photocontrol in cationic polymerizations. Herein, we introduce monophosphonium-doped polycyclic arenes as an organic photocatalyst, which features the high tunability, broad redox window, long excited state lifetime, and excellent temporal control in the cationic reversible addition-fragmentation chain transfer polymerization of vinyl ethers. A correlation of the catalytic performance and the photophysical and electrochemical properties of photocatalysts is also discussed.