The binodal curves of the aqueous two-phase system (ATPS) containing the polyoxyethylene (10) lauryl ether (POELE10, C32H66O11) and three potassium salts (KOH/K2CO3/K3PO4) were determined at the temperatures (288.15, 293.15, 303.15, and 308.15) K. The three experience equations were used to fit the binodal data for the studied systems, and a satisfactory correlation effect was obtained. The effect of salts on the binodal curves for the investigated systems was discussed by the effective excluded volume (EEV), and we found that the salting-out effect is mainly influenced by valence of anion of salts. The salt containing the higher valence of anion has a stronger phase-forming ability than that with a lower charge of anion. The liquid-liquid equilibrium (LLE) data for the investigated systems were determined and correlated by the Othmer-Tobias and Bancroft equations. The effect of the change of temperature on the binodal curves and tie-lines was also studied through the analysis of the EEV values and cloud point (CP) figure. The increase in temperature leads to the strengthening hydrophobicity of POELE10 that drive more water transferring from the top phase to the bottom phase, which means the phase-forming ability of the whole systems was strengthened. Thus, the critical concentration of POELE10 and salts for forming ATPS decreases with the rising temperature.