Alkene carbonylation holds the promise to provide atom-efficient, clean routes for the production of ester, aldehyde, amide, etc., and CO insertion followed by C–C bond coupling is an ideal route for ketone synthesis. However, alkoxycarbonylation and hydroformylation, in which ester and aldehyde are produced via CO insertion followed by C–O and C–H bond formation, respectively, overwhelmingly dominate the alkene carbonylation reactions. Herein, a promising approach to realize the ethylene carbonylation followed by C–C bond formation to produce 3-pentanone was developed by coupling with alcohol dehydrogenation–transfer–hydrogenation (DTH) reactions on a ceria-supported Rh catalyst. The interfacial Lewis acid–base pair site (Rhδ+–O–Ce3+–Ov), which is constituted by Lewis acidic Ce3+–Ov (oxygen vacancy) and basic interfacial oxygen of Rhδ+–O–Ce3+, dissociatively activates alcohol and its DTH reactions, which promotes the tandem reaction of ethylene carbonylation and C–C coupling to 3-pentanone. This route provides an alternative way to selectively synthesize higher ketones by one-step olefin carbonylation.