The excited-state proton transfer (ESPT) dynamical behavior of aloesaponarin I (ASI) was studied using density functional theory (DFT) and time-dependent DFT (TDDFT) methods. Our calculated vertical excitation energies based on TDDFT reproduced the experimental absorption and fluorescence spectra well [Nagaoka et al. J. Phys. Chem. B, 117, 4347 (2013)]. Two intramolecular hydrogen bonds were confirmed to be strengthened in the S1 state, which makes ESPT possible. Herein, the ESPT process is more likely to happen, along with one hydrogen bond (O1–H2⋯O3). Qualitative analyses about charge distribution further demonstrate that the ESPT process could occur because of the intramolecular charge transfer. Our constructed potential energy surfaces of both S0 and S1 states show that a single proton transfer reactive is more reasonable along with the intramolecular hydrogen bond (O1–H2⋯O3) rather than O4–H5⋯O6 in the S1 stated potential energy surface. Then, ASI-SPT* decays to the ground state with a 640 nm fluorescence; subsequently, the ASI-SPT form shows that reverse ground state single-proton transfer back to the ASI structure occurs. Particularly, dependent on relatively accurate potential energy barriers among these excited-state stable structures, we confirmed the excited-state single proton transfer process rather than using the controversial nodal plane model.