The microstructure of Triton X-100 (TX-100)/poly (ethylene glycol) (PEG) complex has been investigated by fluorescence resonance energy transfer (FRET), dynamic light scatter (DLS), freeze-fractured transmission electron microscopy (FF-TEM) and H-1 NMR technology. The nonionic surfactant TX-100 and pyrene are employed as energy donor and acceptor respectively, and the average distance between them is calculated quantitatively in the systems of TX-100/PEG with different molecular weights (MW). The results of FRET study indicate that the presence of PEG leads to the separation of donor and acceptor in TX-100 micelle, suggesting that PEG chains insert into TX-100 micelles making the microstructure of PEG-bound TX-100 aggregates looser than that of free micelles, which is independent of the MW of PEG. However, FF-TEM, DLS and H-1 NMR studies show that the morphology of TX-100/PEG complex depends on the MW of the polymer: PEG with shorter chain (MW < 2000 Da) insert into and wrap around TX-100 micelles and form sphere-like complex, while that with longer chain (MW > 2000 Da) would interact with numbers of TX-100 micelles and form coral-shaped clusters. In addition, the effects of temperature and alcohol on the microstructure of TX-100/PEG complex are studied. (c) 2007 Published by Elsevier Ltd.