A transition-metal-free single electron transfer reaction has been developed for the synthesis of [D3]-alkenes from terminal alkynes using sodium dispersions as the electron donor and EtOD- d1 as the deuterium source. Both reagents are cost-effective and bench-stable. This practical method exhibits remarkable terminal alkyne selectivity and exclusive alkene selectivity. Excellent deuterium incorporations and yields were achieved across a broad range of terminal alkynes without olefin isomerization. Of note, this reaction is highly solvent dependent. n-Hexane provides unique enhancement to this reductive deuteration process.