Dendrimers have been previously shown to provide significant advantages in both excited-state energy transfer and charge transfer. However, this architecture causes one of the charges to be encapsulated and thus not available for charge separation over long distances. We conceived dendron−rod−coils as scaffolds that could have the architectural advantage of the dendrimers, while still providing a possible conduit for charge separation. In this study, we have designed and synthesized dendron−rod−coil-based donor−chromophore−acceptor triads and have compared these with dendron−rod and rod−coil diads. We have then evaluated the relative abilities of these molecules in photoinduced charge transfer. Our studies reveal that dendron−rod−coil could indeed be the ideal architecture for efficient photoinduced charge separation.