The direct oxidative α‐alkoxylation of carbonyl compounds is very important, highly desirable but relatively rare. A general and convenient approach has been developed to prepare 3‐oxy‐4‐isochromanones by copper‐catalyzed α‐C(sp3)−H alkoxylation of 4‐isochromanones with alcohols. The key features are easily available starting materials, mild reaction conditions, broad substrate scope, and excellent regioselectivity.