An efficient silver‐catalyzed stereoselective trans‐addition of 4‐hydroxycoumarins to haloalkynes under ambient air is described, allowing the straightforward synthesis of vinyl halides. The late‐stage nitration of the resulting products with silver nitrate proceeded with retention of configuration, affording a series of nitroalkenes in good yields. Additionally, DFT calculations were employed for mechanistic studies, and a possible mechanism for the Ag(I)‐catalyzed addition was proposed. Two silver medals: An efficient silver‐catalyzed stereoselective transaddition of 4‐hydroxycoumarins to haloalkynes afforded a number of exclusive addition products in high yields. Nitration of the addition products provided an approach to synthesize nitroalkenes. Additionally, based on the results from DFT calculations, a possible mechanism for the Ag(I)‐catalyzed addition was proposed.