The tautomeric properties of favipiravir, a promising anti-COVID-19 drug, were investigated experimentally for the first time by using molecular spectroscopy (UV–Vis absorption, fluorescence and NMR), as well as DFT quantum–chemical calculations. According to the obtained results, the enol tautomer is substantially more stable in most of the organic solvents. In the presence of water, a keto form appears to be favored due to the specific solute–solvent interactions. Upon the addition of alkaline-earth-metal ions, deprotonation and complexation occurred simultaneously, giving the formation of 2 : 1 ligand : metal complexes. According to the theoretical simulations, the metal ion is captured between the carbonyl groups as a result of the size–fit effect.