A step-economical and efficient strategy for the enantioselective synthesis of tetradeuterated γ-nitroketones using a cost-effective and readily available deuterium source is highly desirable. Herein, we report a nickel-catalyzed one-pot H/D exchange and highly enantioselective Michael addition of α,β-unsaturated 2-acyl imidazoles with nitromethane in the presence of D2O. This protocol demonstrates excellent efficiency, high enantioselectivity, and a broad substrate scope, offering a practical and versatile approach to accessing deuterium-labeled compounds.