In this study, the solubility of naphthalene was used to demonstrate the dissolubility of three top aqueous two-phase systems (ATPSs) comprising polyethylene glycol (PEG) 1000, PEG 1500, and PEG 2000, respectively, mixed with ammonium sulfate (NH 4 ) 2 SO 4 . First, the liquid−liquid equilibrium data were obtained for the three individual ATPSs. Under the condition of 1 mg naphthalene in a 1 mL individual top phase of the ATPSs at 298 K, the measured dissolubilities with compositions of 20 wt % ammonium sulfate and 20 wt % PEG 1000, 1500, and 2000 against naphthalene were 4.19, 4.80, and 5.04 mmol•L −1 , respectively. It was demonstrated that the dissolubility of naphthalene in the top phase of ATPS positively correlates with the contents of PEG, salt, and both (PEG and salt), with average correlation coefficients of 0.9817, 0.9978, and 0.9588, respectively. The dissolubilities of the top phases of the three ATPSs against naphthalene were compared and revealed to be within 98−163% of those of 13 selected common solvents, indicating that their performance can be further fine-tuned. The results obtained in this study highlight characteristics of the ATPSs that render them suitable for use as solvents, in addition to their well-known use as separation candidates.