This work was supported by the Associate Laboratory for Green Chemistry-LAQV, which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019). FCT/MCTES is also acknowledged through the National Portuguese NMR Network RECI/BBB-BQB/0230/2012. A.A.-A. is grateful for the postdoctoral fellowship from Fundacion Alfonso Marti0n Escudero. The multistate of chemical species generated by 4′-hydroxy-3,2′-furanoflavylium is similar to that of anthocyanins and related compounds. This furanoflavylium multistate system was fully characterized by UV-visible and NMR spectroscopy, allowing determination of the respective equilibrium and rate constants. In contrast to the multistate generated by flavylium cations derived from anthocyanins and related compounds, the furanoflavylium multistate is characterized by much slower hydration and tautomerization (pyran ring opening-closing). In addition, the cis-trans isomerization of the chalcones of this system (2′-hydroxyaurones) is extremely slow when compared with anthocyanins. The observed similar order of magnitude for tautomerization and isomerization rate constants leads to peculiar kinetics from the flavylium cation (pH = 1) to the stable trans-chalcone (higher pH values). The hemiketal appears and disappears during the first stages of the kinetics, which gives the intermediate cis-chalcone (pseudo-equilibrium). This last species disappears in a much slower process, as fully characterized by 1 H NMR, to give the final trans-chalcone. publishersversion published