The layer-by-layer deposition of thin films of CdTe nanoparticles and three different polyelectrolytes has been investigated. Photoluminescence spectra were used to monitor the energy transfer properties within the films. As the number of bilayers in a thin film was increased a decrease in the energy of the light emitted was observed. The wavelength change is a two-stage process. Deposition of the first one to two bi-layers of a thin film produced a sharp energy change (626 nm to 637 nm with the addition of a single bi-layer) whereas deposition of subsequent bi-layers produced a more gradual energy change (642 nm–646 nm with the addition of 5 bi-layers). A space-filling mechanism is suggested to account for these changes; smaller nanoparticles penetrate the earlier levels of a thin film and increase the inter-particle energy transfer opportunities within the layers.