Selective intermolecular oxidative cross-coupling of enolates, which is a bond-forming reaction between carbanion equivalents, remains as an unsolved issue despite its potential utility for the direct synthesis of unsymmetrical 1,4-diones. The main difficulty derives from the unavoidable homo-coupling. Our strategy depends on the selective one-electron oxidation of one enolate to afford an electrophilic carbonyl alpha-radical species, followed by trapping with another enolate. The present study demonstrates the selective oxovanadium(V)-induced cross-coupling between boron and silyl enolates.