Excited state intramolecular proton transfer (ESIPT) in a novel salicylidene sal-3,4-benzophen chromophore is studied by white-light femtosecond pump−probe and time-resolved fluorescence techniques, as well as by theoretical calculations under the time dependent density functional theory framework. We show that when the sal-3,4-benzophen chromophore (in enol form) is excited (at 390 nm) to the cisenol* form, it is quickly converted to the hot cis-keto* (hK*) form due to the fast ESIPT process (τ ESIPT = 150 fs). Subsequently, cooling from the hot cis-keto* (hK*) to cold cisketo* (cK*) state takes place with a characteristic time constant of ∼600 fs, with following relaxation decay time of 37 ps related with the photodynamic from sal-3,4-benzophen due to the occurrence of the cis → trans photoisomerization and intersystem crossing mechanisms. Finally, we observed the fluorescence emission from the cis-keto* at 575 nm. The dynamics of the optical process was modeled using rate equations with the proper energy level diagram and supported by theoretical calculations.