An efficient transformation towards propynoates and propynenitriles is herein described. The practical methodology was conducted at low temperature (–78 or –60 °C) in a one-pot manner with the assistance of base rather than any transition metal catalysts. The base-induced protocol exhibits good functional group tolerance (up to 28 examples) and high efficiency (up to 92% yields) towards substituted acetylenes of great synthetic significance, which was also well demonstrated by the gram-scale reactions.