In the tautomeric Schiff bases, derived from 7-hydroxyquinoline, two competitive channels are possible upon excitation of the enol tautomer, namely proton transfer (PT) through intramolecular hydrogen bonding to the corresponding keto form and trans–cis isomerization around the azomethine double bond. The former leads to switching, based on twist-assisted excited state intramolecular PT, where the long-range proton transfer can occur as a targeted process. The latter, determined by the flexibility of the crane part, reduces the efficiency of the main targeted process. In previously studied molecular switches based on the 7-hydroxyquinoline skeleton, only the intramolecular PT photo-process undergoing from the excited enol form towards the keto tautomer, which is in most cases barrierless, has been discussed. Therefore, in the current study, the ground state PT properties and isomerization of (E)-8-((phenylimino)methyl)quinolin-7-ol and (E)-8-(((pentafluorophenyl)imino)methyl)quinolin-7-ol are investigated in depth using the MP2 methodology, while the excited state energy profiles are calculated with the ADC(2) method. The obtained results are discussed in light of the existing experimental data.