Herein, we report a photocatalytic method for the selective functionalization of α-C(sp3)-H bonds adjacent to the nitrogen atom in amides. By harnessing a synergistic combination of hydrogen atom transfer (HAT), consecutive photoinduced electron transfer (ConPET), and reductive radical-polar crossover, we efficiently incorporated high-value electrophiles, including CO2, 13CO2, and deuterium, at the α-N position. The transformation proceeds in moderate to high yields across a diverse range of amides, representing a significant advancement in both isotopically labeled α-amino acid synthesis and amide deuteration.