We demonstrated herein a versatile protocol for visible-light-induced decarboxylative alkylations enabled by electron-donor acceptor complex. An array of primary, secondary, tertiary and amino acid-derived redox-active esters (RAEs) were all amenable substrates to undergo radical decarboxylation to be coupled with a diverse range of nucleophiles, creating diverse C(sp 3 )À C(sp 3 ) and C(sp 3 )À C(sp 2 ) bonds with high efficiency. It is worth noting that Katritzky's salt and Togni's reagent were also suitable substrates, affording deaminative alkylation and trifluoromethylation products in high yields. Additionally, a one-pot two-step telescoped procedure and continuous-flow process further increase the synthetic utility of this catalytic system.