The nanosecond pulse radiolysis technique has been applied to study the rate constants for charge transfer and substitution reactions of radical ions. Electron transfer from biphenyl anion to styrene derivatives shows a correlation with the reduction potential of the acceptors expected from the Marcus theory. The positive charge transfer from biphenyl cation to the same acceptors shows a much larger rate constant, suggesting a considerable shift of the free energy relationship to the positive side of Go. The substitution reaction of fluorenone anion with organic halides shows an SN2 character, while that of diethyl fumarate shows electron transfer nature. The dimerization of radical anions has been proven for benzophenone and fluorenone, when their lifetime of the parent anions are prolonged by countercations.