Chiral polycyclic aromatic hydrocarbons (PAHs) are expected to have unusual physical properties due to their chirality and expanded pi-conjugated system. Indeed, PAHs are promising compounds as chiral recognizers and organic semiconductors. Therefore, an efficient method for the synthesis of chiral PAHs is strongly desired. In contrast to helically chiral PAHs, there are only limited examples of the enantioselective synthesis of axially chiral PAHs. Herein, we report the catalytic enantioselective synthesis of benzo[b]fluoranthene-based axially chiral PAHs in excellent yields and enantioselectivities (up to >99%, >99% ee) by regioselective cleavage of the sterically hindered C-C bond of biphenylenes. The consecutive cyclizations could provide polycyclic PAHs with two chiral axes. The obtained chiral PAHs have high epsilon values (up to epsilon = 8.9 x 10(4)), quantum yields (up to Phi = 0.67), and circularly polarized luminescence (CPL) property (vertical bar g(lum)vertical bar = up to 3.5 x 10(-3)).