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.