Abstract The effect of protonation on the excited state properties of the three positional isomers of E -5-[2-(pyrid- n -yl)ethenyl]oxazole’s ( n -PyEt-5Ox with n = 2, 3 and 4) was studied in buffered water by spectrophotometric, fluorimetric and chromatographic measurements. The clear shift to the red of the absorption and emission spectra by protonation indicates that the basicity of these compounds increases strongly (by ∼7 pH units) under excitation. Ground state pK a values (around 5) were measured by absorption (for n = 2 and 4) and fluorescence (for n = 3) titration and excited state pK a * values were estimated by application of the Forster cycle. For the compound with n = 3, which displays a rather higher fluorescence lifetime, it was possible to perform a direct fluorimetric titration which showed two inflection points corresponding to pK a (4.77) and pK a * (12.27). Previous works on these compounds had shown a marked deactivating effect of the pyridine n,π * states on the emitting and reactive π,π * states (proximity effect) favouring relaxation by internal conversion with a marked reduction of the competitive fluorescence and trans - cis (E–Z) isomerisation yields, particularly for n = 2 and 4 in non-polar cyclohexane. The new results indicate that the aqueous solvent, and mainly protonation, affect sensibly the spectral, photochemical and photophysical behaviour increasing again the radiative and reactive parameters of compounds with n = 2 and 4. The isomer with n = 3, whose n,π * states play a much smaller deactivating effect, shows a peculiar behaviour with a very low isomerisation yield at acid pH, reasonably due to intramolecular charge transfer from the Ox ring to the PyH + moiety, which hinders the twisting process. All these results are compared with those reported in the literature for the n -styrylpyridine analogues to point out the role of the oxazole group.