The solubility of ibuprofen, a nonsteroidal anti-inflammatory drug (NSAID), is enhanced by synthesizing ibuprofen ester with a water-soluble polymer, poly(ethylene glycol) (PEG), and the product obtained functions as a nonionic surfactant (IBF-PEG800, IP800). The morphology and aggregation behavior of IP800 micelles and IP800/PEG complexes in aqueous solution are investigated by (1)H NMR technology, dynamic light scattering (DLS), isothermal titration calorimetry (ITC), and fluorescence resonance energy transfer (FRET). The microstructure of IP800 micelles is strongly related to the concentration of IP800. IP800 monomers can form looser micelles at relatively low concentrations and much tighter micelles at high concentrations. And the binding model of PEG with looser IP800 micelles dramatically depends on the molecular weight and concentration of PEG: PEG with lower molecular weight (MW < or = 2000 Da) inserts to the interface of the hydrophilic corona and hydrophobic core of IP800 micelles; PEG with higher molecular weight (MW > 2000 Da) binds to the surface of IP800 micelles, and one long PEG chain (6000 < MW < or = 20000 Da) wraps several IP800 micelles. Besides, the ratio of short chain PEG400 to IP800 micelles of the IP800/PEG complex is about 15:1 at a fixed concentration of IP800 (0.05 mM), and for the long chain PEG20000 it is 1:3-1:4.