The oxidative interception of various σ‐alkyl palladium(II) intermediates with additional reagents for the difunctionalization of alkenes is an important research area. A new palladium‐catalyzed oxidative difunctionalization reaction of alkenes with α‐carbonyl alkyl bromides is described, in which the σ‐alkyl palladium(II) intermediate is generated through a Heck insertion and trapped using an aryl C(sp2)H bond. This method can be applied to various α‐carbonyl alkyl bromides, including primary, secondary, and tertiary α‐bromoalkyl esters, ketones, and amides. Indolinone synthesis: A new palladium‐catalyzed oxidative difunctionalization reaction of N‐arylalkenes with primary, secondary, and tertiary α‐carbonyl alkyl bromides proceeds through a radical process and provides indolin‐2‐ones in moderate to excellent yields. The reaction is initiated by a Heck insertion followed by interception of the σ‐alkyl palladium(II) intermediate with aryl C(sp2)H bonds. dppe=1,2‐bis(diphenylphosphino)ethane.