Herein, an efficient strategy to synthesize 2‐unsubstituted terminal 1, 3‐enynes in high yields by bimetallic Pd/Cu‐catalyzed Sonogashira coupling‐elimination reaction of iodobenzenes with 4‐bromobut‐1‐yne was reported. To our knowledge, this is the first report of 4‐bromobut‐1‐yne as an efficient 1, 3‐enynes reagent, and the method is more convenient and cost‐effective than other reported synthetic methods, which are hindered by the laborious preparation of starting materials, the high cost of bromoethene, and the inconvenient handling of gas acetylene.