The excited-state properties of two peryleneimide chromophore end-capped pentaphenylene compounds were investigated in detail using femtosecond transient absorption and single-photon timing experiments. Singlet-singlet annihilation was found to promote one chromophore into a higher excited state and results in the formation of an ultra-short-living intermediate charge-transfer (CT) state in the S-n-S-1 deactivation pathway. In low-polarity solvents, this CT state is found to be energetically higher than the first excited state and thus cannot be populated via one-photon excitation. The observed CT state decoys with a time constant of about I ps to form the lowest singlet excited state. These results demonstrate the potential use of the singlet-singlet annihilation as a novel tool in studying reactions occurring in states that are energetically above the S-1.