The fluorescence properties of double layer-type dendrimers with carbazole as the outer layer and phenylazomethine as the inner layer of the dendron with a zinc porphyrin core were studied. Based on the fluorescence quantum yield (solution), the effect of the bulky dendron to inhibit the interaction of the chromophores was confirmed. Additionally, the efficient light-harvesting property of the double layer-type dendron was revealed by the fluorescence measurement at several excitation wavelengths. These dendrimers were used as an emitting-layer in an OLED device. The electroluminescence of the core porphyrin was observed and it was shown that the double layer-type dendrimer with a luminescent core has the potential to be a hole-transporting/emitting material.