AbstractAn assembly has been synthesised that consists of four units: a meso‐substituted corrole (C3), perylene bisimide (PI), and two electron‐rich triphenylamine (DPA) units. PI is connected through a 1,4‐phenylene bridge to C3, whereas the two DPA units are linked to C3 through a diphenyl ether linkage, which is used for the first time to connect the various moieties. Various synthetic strategies were elaborated, and the chosen one afforded the final system in six steps in an overall yield of 6 %. The resulting assembly, made of three different units, was named a “triad”. Excitation of the corrole (C3) or perylene bisimide (PI) units led to the charge‐separated state DPA‐C3+‐PI− with a rate k>1011 s−1 in benzonitrile and dichloromethane (CH2Cl2) or with k of the order of 1010 s−1 in toluene. The latter charge‐separated state decayed to the ground state with a rate k=1.8×109 s−1 in toluene. In the polar solvents benzonitrile and dichloromethane, recombination to the ground state competes with a charge shift to form the distal charge‐separated state, DPA+‐C3‐PI−, the formation of which occurs with a yield of 50 %. Recombination to the ground state of DPA+‐C3‐PI− occurs with a rate k=5×107 s−1 in CH2Cl2 and k=2×107 s−1 in benzonitrile.