Abstract Herein we report on the selective iron‐catalyzed cross‐coupling reaction of terminal phenylacetylenes with iodo‐aryl derivatives to afford the respective coupling products in the presence of 10 mol% FeCl 2 (bdmd) and 10 mol% [Cu(CH 3 CN) 4 ]BF 4 (bdmd=bis((diphenylphosphanyl)methyl)diphenylsilane). The yields are moderate to good in 1,4‐dioxane or DMF. This is the first example of a well‐defined and fully analysed ferrous complex acting as a precatalyst in Sonogashira cross‐coupling reactions. Notably, FeCl 2 (bdmd) is compatible with reactive substituents such as carbonyl‐, carboxyl‐, hydroxy‐, and amino‐groups, which allows for an effective cross‐coupling reaction in the presence of such functional groups.