The oil-induced aggregation behavior of PEO-PPO-PEO Pluronic P84 [(EO)(19)(PO)(39)(EO)(19)] in aqueous solutions has been systematically investigated by H-1 NMR spectroscopy, freeze-fracture transmission electron microscopy (FF-TEM), and dynamic light scattering (DLS). The critical micellization temperature (CMT) for P84 in the presence of oils decreases with increasing oil concentration. The effectiveness of various oils in decreasing the CMT of block copolymer follows the order m-xylene (C8H10) > toluene (C7H8) > benzene (C6H6) > n-octane (C8H18) > n-hexane (C6H14) approximate to cyclohexane (C6H12). It was found that the amount of anhydrous PO methyl groups increases whereas the amount of hydrated PO methyl groups decreases upon the addition of oils. At low oil concentration, the oil molecules are entrapped by the micellar core, but as the oil concentration increases above a certain value, the micellar core swells significantly as a result of the penetrated oil molecules, and much larger aggregates are formed. Intermolecular rotating-frame nuclear Overhauser effect (ROE) measurements between P84 and benzene were performed at 10 and 40 C. The specific interaction between benzene and the methyl groups of PPO was determined, and it was observed that the interaction site remained unchanged as the temperature was increased.