In this work, we theoretically investigate the properties of excited state process for a novel salicylidene sal-3,4-benzophen (Sal-3,4-B) system, which contains two intramolecular hydrogen bonds (O1-H2[Formula: see text]N3 and O4-H5[Formula: see text]N6). Based on the density functional theory (DFT) and time-dependent DFT (TDDFT) methods, we find these two hydrogen bonds should be strengthened in the S1 state, while the O4-H5[Formula: see text]N6 one could be largely affected upon the excitation process. Analyses about infrared (IR) vibrational spectra about hydrogen bond moieties also confirm this viewpoint. Frontier molecular orbitals (MOs) depict the nature of electronic excited state and support the excited state intramolecular proton transfer (ESIPT) reaction.Two kinds of stepwise potential energy curves of Sal-3,4-B in the S1 state demonstrate that only one proton could be transferred. Also based on constructing potential energy curves, the synergetic situation could be eliminated. Due to the specific ESIPT mechanism for Sal-3,4-B, we successfully explain the previous experiment and provide a reasonable attribution to the second emission peak of experiment.