The factors driving the Ni⁰(binap)/Cu^I(phospherrox) cooperative asymmetric propargylation of aldimine esters are unveiled through DFT calculations. The system is fully explored accounting for conformational complexity and aggregation steps. The activation of the substrates proceeds independently, while the intercatalyst communication occurs both through indirect cooperativity, exchanging the non-innocent MeOCO₂⁻, and through direct cooperation in the stereoselective C–C coupling driven by intercatalyst interactions.