In view of the prominent regulated characteristics of electron-donating substituted julolidine-bis(salicylidene)-1,5-diaminonaphthalene (PQ-BSD) derivatives, we are dedicated to exploring photo-induced excited state behaviors of PQ-BSD in solvents. Given the variational solvent polarities, the geometrical changes, infrared (IR) spectral variations, core-valence bifurcation (CVB) indexes as well as charge reorganizations are focused on based on TDDFT method. The strengthened excited-state hydrogen bonding interactions of both hydrogen bonds fully present the excited state intramolecular proton transfer (ESIPT) tendency. Via constructing potential energy surfaces (PESs), the stepwise excited state intramolecular double proton transfer (ESIDPT) process could be revealed for PQ-BSD fluorophore.