The modular assembly of a directional photoredox-active multidonor-photosensitizer-multiacceptor (Dn-P-Am) architecture is presented. The triad assembly features a central Ru(ii) sensitizer equipped with pendant polymer chains consisting of multiple triarylamine (pTARA) and naphthalene diimide (pNDI) units, respectively. Upon excitation, the efficient formation (>96%) of charge separation (CS) was observed featuring similar CS lifetimes (400 ns) as related molecular triads. In contrast, a significant additional longer-lived CS component (2400 ns, 30%) is observed indicating multiple contributing pathways.