In this paper we demonstrate that multilayer structures with modulated bandgaps can be used for efficient energy transfer and carrier confinement inside a nanostructured film of a light-emitting polymer. The films were produced with the layer-by-layer technique (LbL) with a poly(p-phenylene vinylene) (PPV) precursor and a long chain dodecylbenzenesulfonate ion (DBS). DBS is incorporated selectively into the precursor chain, and with a rapid, low temperature conversion process (100 °C) superstructures with variable HOMO–LUMO gap could be formed along the deposition direction by changing the DBS concentration. Structures with different stair-type energy modulations were produced, which are thermally stable and reproducible, as demonstrated by UV-VIS. absorption measurements. Energy differences of up to 0.5 eV between the lowest and highest conjugated layers inside the stair structure could be achieved, which was sufficient to guide the excitation over long distances to the lower bandgap layer.