The development of chiral compounds exhibiting circularly polarized luminescence (CPL) has advanced remarkably in recent years. Designing CPL-active compounds requires an understanding of the electric transition dipole moment (μ) and the magnetic transition dipole moment (m) in the excited state. However, while the direction and magnitude of μ can, to some extent, be visually inferred from chemical structures, m remains elusive, posing challenges for direct predictions based on structural information. This study utilized binaphthol, a prominent chiral scaffold, and achieved CPL-sign inversion by strategically varying the substitution positions of phenylethynyl (PE) groups on the binaphthyl backbone, while maintaining consistent axial chirality. Theoretical investigation revealed that the substitution position of PE groups significantly affects the orientation of m in the excited state, leading to CPL-sign inversion. Furthermore, we propose that this CPL-sign inversion results from a reversal in the rotation of instantaneous current flow during the S1 → S0 transition, which in turn alters the orientation of m. The current flow can be predicted from the chemical structure, allowing anticipation of the properties of m and, consequently, the characteristics of CPL. This insight provides a new perspective in designing CPL-active compounds, particularly for C2-symmetric molecules where the S1 → S0 transition predominantly involves LUMO → HOMO transitions. If μ represents the directionality of electron movement during transitions, i.e., the "difference" in electron locations before and after transitions, then m could be represented as the "path" of electron movement based on the current flow during the transition.