A method for the radical addition toward N-tosylimines based on light promoted C–H activation by tetrabutylammonium decatungstate is described. The reaction proceeds under irradiation using 400 nm light emitting diodes in conventional glassware. The method can be applied for alkylations (cycloalkanes, ethers, dimethylformamide) and acylation (primary aliphatic aldehydes) of both aromatic and aliphatic N-tosylimines.