A range of catalysts was synthesized; these catalysts contained species analogous to the structures appearing during the various elementary steps in the hydrogenation of alkenes over catalysts of extremely strong one-electron donor centers. The primary catalytic system, gamma-Al2O3-metallic potassium, was modified by naphthalene, anthracene, and perylene vapors to form surface electron donor-acceptor (EDA) complexes. The specific EDA complexes were also prepared by the immobilization of potassium naphthenide on a gamma-Al2O3 surface in amounts relative to the number of surface hydroxyls. The investigated catalysts were tested in the isomerization of 1-pentene and 1-hexene and in the hydrogenation of ethene and propene. The catalytic importance of ion radical species of alkenes formed during their isomerization and hydrogenation over superbasic systems was demonstrated.