A highly stereoselective [Pd]-catalyzed arylation of tert-alkenols, is presented and applied to the synthesis of indenes using intramolecular Friedel–Crafts alkylation sequence. The initial Heck reaction is performed by using water as the green solvent. A simple acid triggers intramolecular alkylation in short reaction times at room temperature. Notably, indenes have been accomplished using a single column chromatography technique. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim