A green H2O-promoted solvent-free hydroamination of electron-deficient terminal alkynes with amines has been developed. All secondary amines, including aliphatic and aromaticamines, gave the corresponding (E)-enamines in good to excellent yields, whereas primary aromaticamines afforded Z-configured products in moderate yields. Propiolates, propyn-1-ones, propynamides, and 1-(ethynylsulfonyl)-4-methylbenzene