In conclusion, a photoredox-mediated deoxygenative radical addition to gem-Bpin/Bpin and gem-Bpin/Ar alkenes has been developed for synthesizing β-keto-gem-diborylalkane and β-keto-gemboryl/Aryl-alkane respectively from abundant aromatic carboxylic acid substrates. To the best of our knowledge, this is the first report of this kind of deoxygenative radical addition to vinyl boronic esters. Mechanistically, triphenylphosphine (PPh 3 ) was used as chemoselective deoxygenative reagent to in-situ generate the acyl-radical which then undergo addition reaction into the vinyl boronic esters. Excellent functional-group tolerance was demonstrated through application to a vast array of substrates, including various naturally occurring, bioactive and drug scaffolds. The usefulness of the obtained compounds is demonstrated by the modular diversification i.e. oxidation of the borul group to access various OH-containing molecules. Importantly, the rapid access to structurally diverse β-keto-gem-diboryl and β-keto-gem-boryl/Aryl alkanes provided by this methodology will likely be of significant value to synthetic chemists, as a site for subsequent diversification.