A visible-light-induced persulfate-promoted cascade phosphorylation/cyclization reaction to access various phosphorylated pyrrolo[1,2-a]indolediones under mild conditions was developed. Notably, the transformation was carried out with diethyl carbonate/H2O as a green medium at room temperature. More impressively, traditional metal catalysts and photocatalysts could be effectively avoided. The reactions are simple to operate, easy to scale up, and have good functional group tolerance.