The present work reports the liquid–liquid equilibrium (LLE) measurements and the construction of binodal curves for polyethylene glycols (PEG) + zinc sulfate/ammonium sulfate + water at three different temperatures (298.15, 303.15, and 308.15 K) and pH values (3.00, 4.70, and 5.21). PEGs with different molecular weights of 2000 g·mol–1 (PEG 2000), 3000 g·mol–1 (PEG 3000), and 8000 g·mol–1 (PEG 8000) were chosen for this study. The phase composition was obtained by measuring the refractive index (n D) and density (ρ) and was further used to obtain the tie-line length (TLL) and the slope of tie-line (STL). The tie-lines are reported at different polymer lengths, pH values, and temperatures. The values of the effective excluded volume (EEV) were employed to analyze the effect of the parameters on the binodal curves. Moreover, the impact of those parameters on the TLL and STL and plait point are discussed and compared with the results of the literature. Furthermore, the binodal curves data and the tie-lines’ ends were fitted using some semiempirical equations with satisfactory results. Finally, the UNIFAC is used to calculate the LLE data of the above system and the adjusted binary group interaction parameters of the model were reported.