In contrast with the well-developed C-C and C-N axial chirality, research focusing on the catalytically asymmetric synthesis of N-N axially chiral compounds is still limited. As a privileged subunit of many antibiotics, the synthesis of N-N axially chiral 3,3′-bisquinazolinones has not been updated with atroposelective construction. Herein, we firstly report a chiral phosphoric acid-catalyzed dual-ring formation strategy leading to the aforementioned compounds with good chemical yields and enantioselectivities. Notably, metal-free reaction conditions are another advantage of this procedure. An efficient, CPA-catalyzed, dual-ring formation strategy to construct a class of N-N axially chiral 3,3′-bisquinazolinones is reported for the first time. Notably, metal-free reaction conditions were also involved in this procedure.