α-Chloroboronic esters are a class of stable multifunctional molecules that show unique applications in pharmaceutical science and organic chemistry. Despite their apparent utility, the synthetic methods of these compounds remain limited. Herein, a novel strategy for the efficient synthesis of α-chloroboronic esters is developed via photoredox-catalyzed chloro-alkoxycarbonylation of vinyl boronic esters. This strategy features the advantages of high atom economy, environmental friendliness, and excellent functional group compatibility and was verified by the cross-coupling of a variety of free alcohols, oxalyl chlorides, and vinyl boronic esters. Control experiments and mechanistic studies indicate that the alkoxycarbonyl radical and α-boryl carbocation are key intermediates in this transformation.