Rhodamine 6G (R6G) molecules were fixed with oriented transition dipole moment in organic-inorganic hybrid film by capillary electrophoresis doping (CED) technique and their orientation distribution was analyzed quantitatively by using single-molecule fluorescence defocused imaging. The CED technique forces R6G molecules to migrate into the hybrid film with the dipole moments aligned parallel to the electric field of CED. An appropriate pre-baking of the film enables stabilization of the oriented molecules inside the film; the doped molecules have the direction of the transition dipole moment parallel with the film plane. (C) 2011 Elsevier B.V. All rights reserved.