Light-mediated polymer cross-linking is frequently employed for the preparation of hydrogels for biomedical applications. However, most photopolymerization processes require activation by UV light or short wavelength visible light, which are highly absorbed by skin and tissue, limiting their uses in transdermal initiation. Herein, we introduce red light-enabled oxime ligation by the in situ photogeneration of aldehydes, which rapidly react with hydroxylamines. We demonstrate efficient polymer cross-linking behind a dermal tissue model by red light initiation. Optimization of the photopolymerization conditions allows for 3D encapsulation of human foreskin fibroblasts with good cell viability postencapsulation.