The redox neutral photocatalytic divergent radical 1,2-difunctionalization of a wide array of structurally varied alkenes with gem-dibromides is presented. On the basis of the electronic effect of alkenes, predictable 1,2-carboxygenation and 1,2-carbohalogenation of alkenes are readily available regardless of steric effect. This protocol affords a practical approach to the biologically important furan skeleton. It is distinguished by good regioselectivity, good functional group compatibility, and late-stage modification and thus signifies an important step forward to divergent radical difunctionalization of alkenes.