Tautomeric equilibria at room temperature were studied for three aromatic imine polyol compounds, previously reported 2-((2-hydroxybenzylidene)amino)-2-(hydroxymethyl)propane-1,3diol 1 and two new compounds 2-(((1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl)imino)methyl)benzene-1,4-diol 2 and 3-(((1,3-dihydroxy-2-(hydroxymethyl)propan-2 yl)imino) methyl)benzene-1,2-diol 3. The dynamic behavior of these equilibria is described by a combination of IR, UV-Vis and NMR spectroscopic measurements with DFT and TDDFT calculations in condensed phase. Among the different approaches, the combination of UV-Vis experimental spectra with the oscillator strengths values estimated from TDDFT calculations allowed for the assessment of the tautomeric populations in DMSO and methanol. These results were consistent with different functionals employed GGA, Hybrid and MetaGGA.