A new palladium‐catalyzed reductive 5+1 cycloaddition of 3‐acetoxy‐1,4‐enynes with CO, enabled by hydrosilanes, has been developed for delivering valuable functionalized phenols. This methodology employs hydrosilanes as the external reagent to facilitate the 5+1 carbonylative benzannulation. The reaction is a conceptually and mechanistically novel carbonylative cycloaddition route for the construction of substituted phenols, through the formation of four new chemical bonds, with excellent functional‐group tolerance. Pd & CO: Employing reductive palladium catalysis enables a new 5+1 carbonylative benzannulation of 3‐acetoxy‐1,4‐enynes with CO and hydrosilanes. This reaction is facilitated by hydrosilanes, and allows straightforward and practical access to functionalized phenols with excellent functional‐group tolerance and high selectivity.