To assign the absolute configuration of target products 3, the single crystal X-ray analysis of 3c was performed (Scheme 4, top) indicating that the reaction proceeded with retention of absolute configuration of the starting aziridine 2. The configuration of all remaining products 3 was established by analogy. Given the obtained very interesting result, the mechanism of developed approach was proposed. The reaction is initiated by the opening of the aziridine ring in 2a by iodide anion acting as nucleophilic catalyst. The iodide 4a interacts with 1a 14 to form photoactive EDA-complex EDA-1 with strong absorption in the visible region (bathochromic shift observed in the UV-VIS spectra of TBAI+1a+2a+DMF). Visible-light irradiation of EDA-1 induces SET and produces radical 5a that undergoes decarboxylation to sp 2 -centered radical 10a. In parallel, anion radical 6a undergoes elimination to benzylic radical 7a that participates in halogen atom transfer to give 4a. It interacts with 2a to give a second EDA-complex EDA-2 (second maximum of absorption observed in the UV-VIS spectra of reaction mixture after 30 minutes). Visible-light irradiation of EDA-2 leads to second SET resulting in radical cation 8a. The latter acts as precursor of benzylic radical 9a that is configurationally stable due to the donation of electrons from the negatively charged nitrogen atom (memory of chirality phenomenon). Cross-coupling between radicals 9a and 10a results in new C-C bond formation that proceeds with retention of configuration at the chiral center originating from aziridine 2a. Notably, both SET processes are facilitated by their irreversibility associated with elimination of iodide anion or carbon dioxide molecule. Importantly, the formation of selected reaction intermediates was confirmed by MS studies. Furthermore, radical 7a was captured by the experiment with TEMPO confirming its formation in the course of the reaction.