Hydrogen bonding between water and tributyl phosphate (TBP) in TBP-CCl_4-H_2Osystem has been studied by ~1H NMR.A new model and an empirical equation have been establishedon the basis of Li’s model and the parameters of hydrogen bond between water and TBP are deter-mined by nonlinear optimization method.In TBP-CCl_4 -H_2O system change of ~1H chemicalshift of water can be satisfactorily explained by the new model and the empirical equation in thewhole concentration range.When the concentration of water in the organic phase is very low,themain existing forms of water are H_2O·TBP and H_2O·2TBP.When the concentration of waterreaches saturation,the main existing form is associated water,but there are still about 20% ofwater existing in the forms of H_2O·TBP and H_2O·2TBP. Hydrogen bonding between water and tributyl phosphate (TBP) in TBP-CCl_4-H_2Osystem has been studied by ~ 1H NMR. A new model and an empirical equation have been established on the basis of Li’s model and the parameters of hydrogen bond between water and TBP are deter-mined by nonlinear optimization method. In TBP-CCl 4 -H 2 O system change of ~ 1H chemical shift of water can be satisfactorily explained by the new model and the empirical equation in thewhole concentration range .When the concentration of water in the organic phase is very low, the main existing forms of water are H 2 O · TBP and H 2 O · 2TBP.When the concentration of waterreaches saturation, the main existing form is associated water, but there are still about 20% of water existing in the forms of H 2 O · TBP and H 2 O · 2TBP.