In this work, the reactive extraction equilibrium of p-nitrophenol (PNP) using tributylphosphate (TBP) dissolved in solvent naphtha and n-octanol has been studied, respectively. The effects of equilibrium pH (pH(eq)), initial TBP, and PNP concentrations on the distribution ratio (D) and the degree of extraction were discussed. The TBP/solvent naphtha showed higher D values than that of TBP/n-octanol. The larger D values were also observed at pH(eq) in the range of 2-5.5. pH(eq) had negligible influences on the structure of TBP/PNP complexes based on IR spectra analysis. TBP mainly reacted with the neutral form of PNP by forming 1:1 (TBP/PNP) complexes through a hydrogen bond between phosphoryl in TBP and hydroxyl in PNP. The model parameters were calculated by fitting the experimental data. D values calculated from the model were in good agreement with experimental ones. In addition, the back-extraction rate was found to be reached 99.9% using 50 mmol.kg(-1) NaOH as stripping agent.