Novel hybrid films of fluorinated hyperbranched polyimide (HBPI) and zinc oxide (ZnO) were prepared via the in situ sol-gel polymerization technique, in which mono-ethanolamine (MEA) was used as the coupling agent between the termini of HBPI and the precursor of ZnO. The hybrid films were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) absorption, ultraviolet visible (UV-vis) absorption, and fluorescent excitation/emission spectroscopy. The films, which originated from the colourless fluorinated HBPI structure and homogeneously dispersed ZnO nanoparticles, exhibited good optical transparency. Furthermore, two kinds of model compounds with and without ZnO and a HBPI film blended with ZnO microparticles were prepared to clarify the fluorescence mechanism in the pristine HBPI and in situ hybrid films. Efficient energy transfer from the ZnO nanoparticles to the aromatic HBPI main chains was observed in the in situ hybrid films, whereas energy transfer occurred only from the locally excited (LE) states to the charge-transfer (CT) state in the HBPI film. These facts demonstrate that the peripheral termini of HBPI are covalently bonded to ZnO particles via the MEA function, which operates as an effective pathway for energy transfer to give intense fluorescent emission. (C) 2010 Elsevier Ltd. All rights reserved.