Abstract Herein, we report a photocatalytic platform to access transient nitrenoids by designing photo‐responsive neutral rhodium‐hydroxamate complexes. Combined experimental and computational mechanistic studies, including electron paramagnetic resonance (EPR) and mass spectrometric analysis, suggest that electrophilic Fischer‐type Rh‐acylnitrenoid intermediates could be generated via photoactivation of corresponding Rh‐hydroxamates via N‐O bond homolysis and redox event. Moreover, catalytic acylnitrenoid transfer was explored toward the amidation of various hydrocarbons, amines, and alcohols to furnish new N−C, N−N, and N−O bonds.