A multitechnique physicochemical comparative investigation involving TDDFT theoretical calculations, steadystate and time-resolved electronic absorption spectra, and electrochemical and photoelectrochemical investigations was carried out on a family of pushpull porphyrinic sensitizers ([5-(40-carboxyphenylethynyl)- 15-(400-methoxy-phenylethynyl)-10,20-bis(3,5-ditert- butylphenyl)porphyrinate]Zn(II) (1) and [5-(40-carboxy-phenylethynyl)- 15-(400-N,N-dimethylamino-phenylethynyl)-10,20-bis- (3,5-di-tert-butylphenyl)porphyrinate]Zn(II) (2) andthenewfluorinated porphyrinic dye [5-(40-carboxy-20,30,50,60-tetrafluorophenylethynyl)- 15-(400-N,N-dimethylamino-phenylethynyl)-10,20-bis(3,5-di-tert-butylphenyl)porphyrinate]Zn(II) (3)) with the aim of identifying the structurally related electronic properties at the basis of efficient interfacial charge separation.We found for all dyes a photoconversion nearly twice more effective for the B band than for the Q band, which could not be explained only by considerations based on the electron collection efficiency but also by a more energetically favorable electron injection from the S2 excited state. The lower photoconversion of the fluorinated dye 3, when compared to dyes 1 and 2, was explained not only by amore difficult absorption on the TiO2 photoanode but also by a lower electron injection efficiency and a less successful hole transfer to the electrolyte, leading to increased charge recombination.