The investigations were made on photoinduced electron transfer (ET) from the singlet excited state of rubrene (1RU*) to p-benzoquinone derivatives (duroquinone, 2,5-dimethyl-p-benzoquinone, p-benzoquinone, 2,5dichloro-p-benzoquinone, andp-chloranil) in benzonitrile (PhCN) by using the steady state and time-resolved spectroscopies. The photoinduced ET produces solvent-separated type charge-separated (CS) species and the charge-recombination (CR) process between RU radical cation and semiquinone radical anions obeys secondorder kinetics. Not only the CS species but also the triplet excited state of RU (3RU*) is seen in the transient absorption spectra upon laser excitation of a PhCN solution of RU and p-benzoquinone derivatives. The comparison of their time profiles clearly suggests that the CR process between RU radical cation and semiquinone radical anions to the ground state is independent from the deactivation of 3RU*. This indicates that the CR in a highly exergonic ET occurs at a longer distance with a large solvent reorganization energy, which results in faster ET to the ground state than to the triplet excited state that is lower in energy than the CS state. Photoinduced ET from 3RU* in addition from 1RU* also occurs when p-benzoquinone derivatives with electron-withdrawing substituents were employed as electron acceptors.