The palladium-catalyzed coupling reaction of N-hydroxyphthalimide esters and styrenes to deliver exclusively (E)-substituted olefins under irradiation with visible light is reported. This method tolerates N-hydroxyphthalimide esters derived from primary, secondary, tertiary as well as benzylic carboxylic acids. Notably, Pd(PPh ) is employed as an inexpensive palladium source and no addition of base or classical photocatalyst is required. Mechanistic studies suggest a light-mediated single-electron reduction of the activated acid by a photoexcited palladium(0) species to access alkyl radicals through decarboxylation.