Carbon-carbon bond formation at α-amino carbon based on α-aminoalkyl radicals is an essential transformation in the synthesis of nitrogen-containing compounds. Recently, some novel photoredox catalytic protocols for this goal have been developed, in which α-aminoalkyl radicals were generated from a sequential oxidation/α-deprotonation of aromatic tertiary amines. Inspired by these studies and based on our previous works, we have developed the cross-coupling reaction of nitrones with aromatic tertiary amines via visible light photoredox catalysis. This method features a radical addition of α-aminoalkyl radicals to nitrones with advantages of simple operation, mild conditions, atom economy, a broad scope of nitrone substrates; and allows for an easy access to β-amino hydroxylamines, which could be readily converted into vicinal diamines. Compared with the UV-excited organophotosensitizer-promoted coupling reaction of nitrones with tertiary amines, visible light is a more safe and convenient light source, the photo-excited electron transfer (PET) by 1 mol% of Ir-photocatalyst is more efficient. In addition, nitrones exclusively server as excellent radical acceptors thus with a broader range of structures. A general procedure of this coupling reaction is as follows: To a 25 mL Schlenk tube equipped with a magnetic stir bar were added a nitrone (0.30 mmol), a tertiary amine (0.90 mmol), Ir(ppy)₂(dtbbpy)PF₆ (0.003 mmol, 1.0 mol%) and K₂HPO₄ (0.06 mmol, 20 mol%). After being evacuated and backfilled with argon for three times, DMSO (3 mL) was added to the tube. Then the tube was placed approximately 7 cm away from a 12 W blue LEDs, and the reaction mixture was stirred at r.t. under an argon atmosphere for 24 h. The reaction was quenched with saturated aqueous NaHCO₃ (25 mL), and the mixture was extracted with dichloromethane (DCM, 20 mL×3). The combined organic layers were washed with brine, dried over anhydrous Na₂SO₄, filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel to afford the desired cross-coupling product β-amino hydroxylamine.