Reported right here is the CO2-facilitated radical sequential (3+2) annulation of 1,6-enynes that proceeds below the concerted catalysis of sulfinate and photocatalyst (PC) to assemble benzo-fused tricyclic scaffolds, that’s, tetrahydrofluorenes and their N-heterocyclic analogues, in typically good yields. This CO2-facilitated methodology permits the secure fragrant teams of 1,6-enynes to endure the radical-addition-induced dearomatization and rearomatization below metal-, exterior oxidant- and base-free circumstances, and incorporates a broad scope of 1,6-enynes substrates, as demonstrated by greater than 60 examples together with a sequence of 1,6-enyne-derivatives of advanced bioactive compounds. Importantly, CO2 as a inexperienced additive is disclosed to be important for attaining this response with good effectivity, demonstrating a brand new position of CO2 on this transformation.