In the present work, we have systematically investigated the dual hydrogen-bonded system 2Z,2′Z-3,3′-(4,4′-methylenebis(4,1-phenylene)bis(azanediyl)bis(1,3-diphenylprop-2-en-1-one)) (abbreviated as L) utilizing quantum chemistry methods, in which the excited-state intramolecular proton transfer (ESIPT) does not conform to the usual stereotype but proceeds along the weakened intramolecular hydrogen bonds (IHBs). Two primary configurations were confirmed to coexist in the ground state (i.e., anti-L and syn-L) by calculating the Boltzmann distribution in three different solvents. Based on the cardinal geometrical parameters involved in IHBs and the interaction region indicator (IRI) isosurface, it can be revealed that the dual IHBs of L were both weakened upon photoexcitation, not least the N₁–H₂⋯O₃ IHB was utterly destroyed in the excited state. The proton-transfer process of anti and syn in three solvents with different polarities has been analyzed by constructing S₀- and S₁-state potential energy surfaces (PESs). It can be concluded that only the single proton transfer behavior along N₁–H₂⋯O₃ occurs in the S₁ state, and the corresponding energy barrier is gradually enlarged with increasing solvent polarity. To further expound the weakened IHB-induced ESIPT mechanism, the scanned PESs connecting the transition state (TS) structures and the initial forms indicate that the ESIPT process is infeasible without the appropriate structural torsion. Our work not only unveils the extraordinary ESIPT process of L, but also complements the results obtained from previous experiments.