The construction of artificial structures through hierarchical self-assembly based on noncovalent interactions, as well as monitoring during the self-assembly process, are important aspects of dynamic supramolecular chemistry. Herein we describe the complex dynamics of chiral N,N'-diphenyl dihydrodibenzo[a,c]phenazine derivatives (S)/(R)-DPAC, whose different assemblies were found to have distinct optical and morphological characteristics. With ratiometric fluorescence originating from vibration-induced emission (VIE), the self-assembly process from kinetic traps to the thermodynamic equilibrium state could be monitored in real time by optical spectrometry. During the morphology transformation from particles to nanobricks, strong circularly polarized luminescence was induced with glum =1.6×10-2 . The excited-state characteristics of the self-assemblies enabled investigation of the relationship between molecular aggregation and conformational change, thus allowing effective monitoring of the sophisticated supramolecular self-assembly process.