Intermolecular electron transfer is investigated in a dye-doped polyelectrolyte (PE) multilayer film. Hollow PE capsules, with a mean diameter of 2 mum, were prepared by stepwise adsorption of a pyrene (PY)-labeled polyanion and various polycations onto charged colloids and subsequent dissolution of the colloidal core. The high concentration of dye molecules within the capsule wall and the control of the medium polarity on a nanometer length scale are proposed to facilitate light-induced charge separation over distances of a few nanometers. In particular, a PY-labeled poly(styrene sulfonate) (PSS-PY) has been synthesized and used as polyanion for the polyelectrolyte capsule preparation. A polarity gradient across the wall of the PE shells is assumed to be achieved by adsorbing diverse polycations at different film positions. The high effective film area followed by high optical density of the PE capsule solution enables time-resolved optical spectroscopy. Using pulsed excited state absorption (ESA) the transient absorption peaks of the radical anion and cation state of pyrene were measured, respectively. In the presence of additional electron donor (or acceptor) molecules in the capsule solution the pyrene anion (cation) is observed in the ESA spectra, while both transient states are seen if no additional molecules are present. These results are interpreted as an electron transfer from pyrene to the donor (acceptor) molecule or between two pyrene molecules. An asymmetry of the electron donor and electron acceptor efficiency was observed when multilayer shells were used that are supposed to carry an internal polarity gradient.