We have investigated photoinduced electron transfer and related processes from the higher excited electronic state (S 2 ) of Zn-porphyrin-imide acceptor directly linked supramolecular systems (ZP-I) designed especially for the critical studies of the energy gap law (EGL) of the charge separation (CS) from the S 2 state and solvent effects upon EGL. We have confirmed the modification of the EGL by change of solvent polarity from acetonitrile (ACN), tetrahydrofuran (THF) to toluene (Tol) and methyl-cyclohexane (MCH), from rather typical bell-shaped one in ACN to that with less prominent normal region and prominent inverted region with moderate slope extending over wider range of -ΔG C S values in nonpolar solvent MCH. We have demonstrated that these solvent effects upon EGL affect delicately various radiationless relaxation processes from S 2 state. We have examined also effects of the hydrogen bonding solvent ethanol (EtOH) on the EGL for CS and found very specific effect controlling the CS reaction and related processes.