Multistep organic synthesis enables conversion of simple chemical feedstocks into a more structurally complex product that serves a particular function. The target compound is forged over several steps, with concomitant generation of byproducts in each step to account for underlying mechanistic features of the reactions (e.g., redox processes). To map structure-function relationships, libraries of molecules are often needed, and these are typically prepared by iterating an established multistep synthetic sequence. An underdeveloped approach is designing organic reactions that generate multiple valuable products with different carbogenic skeletons in a single synthetic operation. Taking inspiration from paired electrosynthesis processes that are widely used in commodity chemical production (e.g., conversion of glucose to sorbitol and gluconic acid), we report a palladium-catalyzed reaction that converts a single alkene starting material into two skeletally distinct products in a single operation through a series of carbon-carbon and carbon-heteroatom bond-forming events enabled by mutual oxidation and reduction, a process that we term redox-paired alkene difunctionalization. We demonstrate the scope of the method in enabling simultaneous access to reductively 1,2-diarylated and oxidatively [3 + 2]-annulated products, and we explore the mechanistic details of this unique catalytic system using a combination of experimental techniques and density functional theory (DFT). The results described herein establish a distinct approach to small-molecule library synthesis that can increase the rate of compound production. Furthermore, these findings demonstrate how a single transition-metal catalyst can mediate a sophisticated redox-paired process through multiple pathway-selective events along the catalytic cycle.