A photooxidative C-C double bond cleavage of electron-deficient β-enaminocarbonyl compounds possessing a silyl group at the α-position to the nitrogen atom using methylene blue (MB) as the photosensitizer was explored. Photochemically generated 1O2 was added across the CC bond with the aid of a tethered silyl group to cleave it and form N-formylamines. This reaction protocol exhibited compatibility with numerous β-enaminocarbonyl substrates, including those with various N-alkyl, N-benzyl and N-aryl substituents.