Best of both worlds: Organocatalytic SN1‐type reactions promoted by indium(III) salts were performed with activated benzylic and benzhydrylic substrates. High ee values and moderate diastereomeric ratios were obtained. The presence of a 4‐NMe2Ph group, which is useful for further transformations, is essential for obtaining high yields. The synergy of indium(III) salts with organocatalysis is a useful strategy for stereoselective transformations.