The combination of electron-rich and electron-poor moieties in conjugated molecules is frequently utilized in order to red shift the absorption spectrum and improve photon harvesting in bulk heterojunction photovoltaic devices. In this study we characterize a conjugated thiophene dendrimer that has an electron-withdrawing core and electron-rich dendrons in order to investigate the effects of this design approach on the salient properties that influence the performance of photovoltaic devices with this dendrimer donor. Beside the absorption onset, these properties are the morphology of dendrimer:fullerene films and the dynamics of photoinduced carrier generation and loss. For comparison we also characterize a control dendrimer with the same structure but without the electron-withdrawing core. In addition to lowering the band gap by ca. 0.5 eV, the electron-withdrawing core also planarizes the dendrimer resulting in enhanced order in bulk heterojunction films. We observe longer photocarrier lifetimes in this ordered structure compared to the films of the predominantly amorphous control. The characterization of dendrimer:fullerene bulk heterojunction photovoltaic devices shows no voltage loss despite the decreased absorption onset. The properties of the device are consistent with the improved photocarrier lifetimes, but they are limited by a low short-circuit photocurrent density. We attribute this to electron confinement in the core that hinders transfer to the fullerene acceptor.