Transient dc conductivity is used to observe high-mobility ions in laser photolysis and pulse radiolysis of cyclohexane and decalins. While in decalins the scavenging of the de conductivity signal from these ions by solutes is a pseudo-first-order reaction, in cyclohexane the behavior is more complex and is indicative of the involvement of two species. This bimodality is rationalized in terms of a dynamic equilibrium between the conformers of the solvent radical cation. A similar equilibrium between the isomer radical cations of decalin is needed to account for the results on photoinduced conductivity in the mixtures of cis- and trans-decalin. In both of these cases, the mechanism of the equilibrium is the reversible charge transfer.