We have previously obtained significant results on the cycloalumination of olefins with EtAlCl2 in the presence of magnesium and Cp2ZrCl2 or Cp2TiCl2 catalyst. Here we report the development of an efficient one-pot catalytic method for the synthesis of tertiary alcohols from AlCl3, arylolefins, and ketones under the action of Cp2TiCl2. The developed method for producing tertiary alcohols has a general character and allows to convert styrene and substituted styrenes (ortho-, para-methylstyrenes) into aryl-substituted tertiary alcohols with yields up to 76% in the reaction with acetone or methylethylketone. We assume that the reaction proceeds through the formation of titanacyclopropane intermediate.