Asymmetric synthesis of quinoline-naphthalene atropisomers with fully blocked ortho positions has been developed by a two-step strategy, which contains a chiral phosphoric acid-catalyzed Povarov reaction and a DDQ oxidation reaction. This method provides facile access to diverse functionalized quinoline-naphthalene atropisomers with one or two chiral axes in excellent yields (≤98%) and excellent enantioselectivities (≤99% ee).