A reactivity pattern for C3-arylation of 9-MeO-phenanthrene has been established for the first time by using 2-naphthyl amines as coupling partners. A series of phenanthrene- and naphthalene-based multifunctionalized polycyclic aromatic hydrocarbons have been obtained in good to excellent yields. Alternative C10-arylation of 9-MeO-phenanthrene has also been accomplished, using 2-naphthalenol derivatives as coupling partners. Trifluoroacetic acid is found crucial for the regioselectivity. Density functional theory calculations and electrochemical analyses have been performed to rationalize the reaction mechanism.