The olefin aziridination reactions catalyzed by copper and silver complexes bearing hydrotris(pyrazolyl)borate (Tpx) ligands have been investigated from a mechanistic point of view. Several mechanistic probe reactions were carried out, specifically competition experiments with p-substituted styrenes, stereospecificity of olefins, effects of the radical inhibitors, and use of a radical clock. Data from these experiments seem to be contradictory, as they do not fully support the previously reported concerted or stepwise mechanisms. But theoretical calculations have provided the reaction profiles for both the silver and copper systems with different olefins to satisfy all experimental data. A mechanistic proposal has been made on the basis of the information that we collected from experimental and theoretical studies. In all cases, the reaction starts with the formation of a metal-nitrene species that holds some radical character, and therefore the aziridination reaction proceeds through the radical mechanism. The silver-based systems however hold a minimum energy crossing point (MECP) between the triplet and closed-shell singlet surfaces, which induce the direct formation of the aziridines, and stereochemistry of the olefin is retained. In the case of copper, a radical intermediate is formed, and this intermediate constitutes the starting point for competition steps involving ring-closure (through a MECP between the open-shell singlet and triplet surfaces) or carbon-carbon bond rotation, and explains the loss of stereochemistry with a given substrate. Overall, all the initially contradictory experimental data fit in a mechanistic proposal that involves both the singlet and the triplet pathways. © 2012 American Chemical Society.