The organic superbase P-4-t-Bu catalyzes the direct anti-Markovnikov addition of alcohols to aryl alkenes to access valuable beta-phenethyl ethers. A diverse substrate scope of aryl alkenes and alcohols is demonstrated, including heterocyclic systems and unprotected aminoalcohols. Mechanistic studies reveal that the reaction is under equilibrium control and extensive comparisons to common inorganic bases indicate that the broad reaction scope is uniquely enabled through the use of the organic superbase.