Developing a step-economical approach for efficient synthesis of α,β-deuterio aryl ethylamines (α,β-DAEAs) with high deuterium ratios using an easy-to-handle deuterated source under ambient conditions is highly desirable. Here we report a room-temperature one-pot two-step transformation of aryl acetonitriles to α,β-DAEAs with up to 92% isolated yield and 99% α,β-deuterium ratios using D