A novel self-assembled (SA) film of a functional dendritic molecule, hyperbranched conjugated poly(phenylene vinylene) (SPPV), is obtained through the covalent bond linkage on a hydrophilic substrate (e.g., mica). The self-assembling process of the film is investigated in detail by UV-vis and fluorescence spectroscopy, and the morphology of the films are observed by atomic force microscopy. Hyperbranched molecules require longer times for forming highly ordered and homogeneous molecular films (several days) compared to small molecules. Excimers formed from the excited state of SPPV in these SA films can be detected by their fluorescence properties. The difference of fluorescence properties between the SPPV SA film and spin-coating film shows that the SA film is ordered and homogeneous. Finally, the photovoltic response is reported for these SA films.