Photoinduced charge separation of a phenothiazine anthraquinone dyad 1 with a rigid bicyclo[2.2.2]octane spacer was investigated by means of picosecond and nanosecond transient absorption and time-resolved ESR spectroscopies. Irradiation of the anthraquinone chromophore in 1 produced the charge-separated (CS) state in THE. Time constants of the formation and the decay of the CS state were determined to be 1.3 ns and 1.0 mu s, respectively. Time-resolved ESR showed spin-polarized all-emission signals due to the formation of the CS state via the triplet mechanism.