Tautomerism of pyrazolo[3,4-b]quinoline (PQ) was studied using electronic absorption and emission spectroscopies in various polar and nonpolar solvents. The absorption spectra of the tatutomers were modeled, and the respective bands were assigned using ab initio quantum mechanical calculations. Temperature-dependent absorption spectra showed the dynamic equilibrium of the two species, which were observed only in aliphatic solvents. The anomalous relative populations of the tautomers were explained by the stabilizing effect of the specific PQ-hydrocarbon interactions. Excited-state intramolecular proton transfer (ESIPT) was proposed to explain the measured fluorescence spectra. Hydrogen bonds that are formed in methanol and benzene were shown to strongly influence the nature of both the absorption and emission spectra.