A direct intramolecular anti-Markovnikov hydroetherification reaction of alkenols is described. By employing Catalytic quantities of commercially available 9-mesityl-10-methylacridinium perchlorate and 2-phenyl-malononitrile as a redox-cycling source of a H-atom, we report the anti-Markovnikov hydroetherification of alkenes with complete regioselectivity, In addition, we present results demonstrating that this novel catalytic system can be applied to the anti-Markovnikov hydrolactonization of alkenoic acids.