Visible-light-mediated photoredox reactions have recently emerged as a powerful means for organic synthesis and thus have generated significant interest from the organic chemistry community. Although the mechanisms of these reactions have been probed by a number of techniques such as NMR, fluorescence quenching, and laser flash photolysis and various degrees of success has been achieved, mechanistic ambiguity still exists (for instance, the involvement of the chain mechanism is still under debate) because of the lack of structural information about the proposed and short-lived intermediates. Herein, we present the detection of transient amine radical cations involved in the intermolecular [3 + 2] annulation reaction of N-cyclopropylaniline (CPA, 1) and styrene 2 by electrospray ionization mass spectrometry (ESI-MS) in combination with online laser irradiation of the reaction mixture. In particular, the reactive CPA radical cation 1+•, the reduced photocatalyst Ru(I)(bpz)3+, and the [3 + 2] annulation product radical cation 3+• are all successfully detected and confirmed by high-resolution MS. More importantly, the post-irradiation reaction with an additional substrate, isotope-labeled CPA, following photolysis of 1, 2, and Ru catalyst provides strong evidence to support the chain mechanism in the [3 + 2] annulation reaction. Furthermore, the key step of the proposed chain reaction, the oxidation of CPA 1 to amine radical cation 1+• by product radical cation 3+• (generated using online electrochemical oxidation of 3), is successfully established. Additionally, the coupling of ESI-MS with online laser irradiation has been successfully applied to probe the photostability of photocatalysts.