The time-dependent spectral properties of a rigid, extended system consisting of three pentaphenylene units end-capped with perylene monoimide were investigated in detail by femtosecond transient absorption and single photon timing measurements. In polar solvents, the molecular system shows the occurrence of photoinduced charge transfer. Upon gradually increasing the excitation power, annihilation involving two states with charge-transfer character has been observed. Quantum-chemical calculations performed on the system consisting of two pentaphenylene units end-capped with perylene monoimide strongly support the experimental data.