In the present study, the novel synthesis of tert-indole-3-carbinols is reported through the DDQ-mediated oxidation of the allylic C-H bond/aromatization/hydroxylation at the indolyl carbon using water as the hydroxyl source. The reaction is highly efficient and high yielding and it works under mild reaction conditions. Furthermore, the synthetic value of such indole-based tert-carbinols is explored through their use as excellent electrophilic methylene surrogates to develop medicinally important unsymmetrical bis(3-indolyl)methanes containing an all carbon quaternary center.