A genetic algorithm (GA)-simplex hybrid approach has been developed for the determination of stability constants using calorimetric and polarographic data obtained from literature sources. The GA determined both the most suitable equilibrium model for the systems studied and the values of the stability constants and the heats of formation for the calorimetric studies. As such, a variable length chromosome format was devised to represent the equilibrium models and stability constants (and heats of formation). The polarographic data were obtained from studies of cadmium chloride and lead with the crown ether dicyclohexyl-18-crown-6. The calorimetric data were obtained from a study of a two step addition reaction of Hg(CN)2 with thiourea. The stability constants obtained using the GA-simplex hybrid approach compare favourably with the values quoted in the literature.