Abstract We examine the photoluminescence properties of three generations of poly(propylenimine) dendrimers and poly(2,5-methoxy-propyloxy sulfonate phenylene vinylene) (MPS-PPV) multilayer films formed by spin-assembly. We observe self-quenching of luminescence with increasing film thickness. For a bilayer system of dendrimer/MPS-PPV, we show an additional terminal dendrimer layer results in films with greater photoluminescence quantum efficiency (PLQE) compared to bilayer films having terminal MPS-PPV layers. Increasing the concentration of the terminal dendrimer layer results in a large increase in PLQE and a spectral red-shift. These changes are a result of increased contact between the dendrimer and MPS-PPV layers through interpenetration.