A series of experiments was conducted in which boron minerals were precipitated by water evaporation from solutions containing boron and potassium, sodium or lithium at 25°C, and boron isotope fractionation accompanying such mineral precipitation was investigated. In the boron-potassium ion system, K Computer simulations for modeling boron mineral formations, in which polyborates were decomposed into three coordinated BO 3 unit and four coordinated BO 4 unit for the purpose of calculation of their boron isotopic reduced partition function ratios, were attempted to estimate the equilibrium constant, K B , of the boron isotope exchange between the boric acid molecule (B(OH) 3 ) and the monoborate anion (B(OH) 4 -). As a result, the K B value of 1.015 to 1.029 was obtained. The simulations indicated that the K B value might be dependent on the kind of boron minerals, which qualitatively agreed with molecular orbital calculations independently carried out.