The synthesis of N-glycosides has received significant attention due to their crucial role in carbohydrate chemistry. Despite considerable advancements were developed in the construction of N-glycosides, methods for the stereoselective construction of 2-deoxy-α-N-glycosides are still limited. Herein, we disclosed a nickel-catalyzed hydroamination of glycals under mild conditions. This transformation could allow for the stereoselective synthesis of an array of 2-deoxy-α-N-glycosides with excellent α-stereoselectivity. Nickel-catalyzed glycosylation reactions, particularly those involving anomeric C(sp3)-metal bond formation, have proven to be an effec-tive and stereoselective strategy for producing various N-glycosides. Additionally, with highlight the application of this reaction, γ-sugar amino acid derivatives were synthesized by one step.