Presented here is a class of novel axially chiral aryl‐p‐quinones as platform molecules for the preparation of non‐C2 symmetric biaryldiols. Two sets of aryl‐p‐quinone frameworks were synthesized with remarkable enantiocontrol by means of chiral phosphoric acid catalyzed enantioselective arylation of p‐quinones by central‐to‐axial chirality conversion. These aryl‐p‐quinones were then used to access a wide spectrum of highly functionalized non‐C2 symmetric biaryldiols with excellent retention of the enantiopurity. A class of atropisomeric aryl‐p‐quinones were efficiently assembled by means of chiral phosphoric acid catalyzed enantioselective arylation of p‐quinones through a central‐to‐axial chirality transfer process. This novel axially chiral framework served as a platform for diversity‐oriented synthesis of a wide range of highly functionalized non‐C2 symmetric biaryldiols with preservation of the chirality.