We report here an organic dye catalyzed direct radical-radical cross-coupling reaction based on the persistent free-radical effect (PRE), which is powered by visible light and does not require any external oxidants or reductants. In this reaction, benzyl trifluoroborates are oxidized by excited-state 4Cz-IPN to generate benzyl radicals, and the resulting boron trifluoride acts as a Lewis acid to reduce the reduction potential of carbonyl compounds. The dual roles of benzyl trifluoroborates enable aldehydes, ketones, diketones, and ketone esters to react with benzyl trifluoroborates to generate various sterically hindered alcohols.