The thermodynamics of the molecular association process between the malvidin-3-O-glucoside and a series of polyphenol derivatives (called 'copigmentation' in food chemistry) were studied in aqueous media. The Gibbs free energy, enthalpy and entropy values were determined by the fluorometric method. A combination of the Job's method with the van't Hoff theory was applied for data evaluation. The results show the exothermic character of the copigmentation process. The change of the enthalpy seems to be the same in every complexation step. However, the decreasing of the entropy term is higher at higher stoichiometries. As a result, the Gibbs free energy changes and, thus, the complex stability decreases quickly with increasing stoichiometry. Quantum-chemical investigation reveals the complexity of molecular interactions between malvidin and polyphenols, which is preferably based on pi-pi and OH-pi interaction moderated by repulsive Coulomb-type interactions.