Herein, we report an efficient photocatalytic startegy for the decarboxylative transformations of redox-active esters to construct C=C, C(sp3)–N, and C(sp3)-X bonds in a single-step. This operationally simple method provides a straightforward access to a variety of protected alkyl amines, alkyl halides and olefins under mild conditions in the absence of metals and photocatalysts. The method can successfully be applied to primary, secondary, and tertiary aliphatic carboxylic acid derivatives. Mechanistic studies indicate that the charge transfer complex (CTC) was formed by nBu4NI with redox-active esters, in which the nBu4NI acted as both an iodine source and an effi-cient electron donor.