The (liquid + liquid) equilibrium (LLE) for the {polyvinylpyrrolidone (PVP3500) + Na2SO3 + H2O} system has been determined experimentally at T = (298.15, 308.15 and 318.15) K. The (liquid + liquid + solid) equilibrium (LLSE) and complete phase diagram of this system were also obtained at T = 298.15 K. The effect of temperature on the binodal curves and the tie-lines for the investigated aqueous two-phase system (ATPS) have been studied. The Merchuk equation and an empirical equation that we proposed in our previous work were used for reproducing the experimental binodal results, and their three fitting parameters were obtained with the temperature dependence expressed in the linear form with (T - T-0) K as a variable. Furthermore, the Othmer-Tobias and Bancroft, a temperature dependent Setschenow-type equation and osmotic virial model, the segment-based local composition models (i.e. the extended NRTL (E-NRTL) and modified NRTL (M-NRTL)) were used for the correlation of the (liquid + liquid) phase behavior of the studied system. Also, we estimated plait point, slope and the length of tie-lines at T = (298.15, 308.15 and 318.15) K. (C) 2014 Elsevier Ltd. All rights reserved.