Four trigonal topology compounds with three diarylamines redox centers and dibenzofulvene as core bridge have been synthesized. Their radical cations exhibit appealing intramolecular electron transfer pathways between three redox centers, depending on their position on the core bridge. By changing such positions (on either 2,7- or 3,6-), and the length of the bridge, the control of the intramolecular electron transfer pathways was achieved through the electron self-exchange route. These processes were investigated by absorption spectroscopy, electron paramagnetic resonance spectroscopy, and (time-dependent) density functional theory calculations. Hole mobility measurements were carried out as well, to correlate the intramolecular electron transfer with the hole-transporting ability for possible applications in optoelectronic devices.