Rare-earth-catalyzed annulation reactions using alkenes via C-H activation offer an atom-efficient approach to constructing cyclic compounds. However, the mechanisms underlying these reactions remain poorly understood, limiting the rational design of related catalytic systems. Recently, Hou and Cong reported an unprecedented example of rare-earth-catalyst-controlled diastereodivergent asymmetric [3 + 2] annulation of aromatic aldimines with alkenes. To elucidate the mechanisms and the origins of diastereo- and enantioselectivity, density functional theory calculations were performed. The results revealed that the styrene insertion step determines the stereoselectivity. Styrene insertion follows a similar metal-styrene interaction pattern across different catalysts. Specifically, during