Rates of Diels-Alder cycloaddition of anthracenes with p-benzoquinone and its derivatives as well as rates of hydride-transfer reactions from 10-methyl-9,10-dihydroacridine to the same series of p-benzoquinones are accelerated significantly in the presence of metal ions in acetonitrile. An extensive comparison of the catalytic effects of metal ions in electron transfer from one-electron reductants (cobalt tetraphenylporphyrin and decamethylferrocene) to p-benzoquinones with those in the Diels-Alder reactions of the quinones as well as the hydride-transfer reactions has revealed that the catalysis of metal ions in each case is ascribed to the 1:1 and 1:2 complexes formed between the corresponding serniquinone radical anions and metal ions. The transient absorption and ESR spectra of the serniquinone radical anion-metal ion complexes are detected directly in the electron-transfer reduction of p-benzoquinone derivatives in the presence of metal ions. The catalytic reactivities of a variety of metal ions in each reaction are well correlated with the energy splitting values of pi(g) levels because of the complex formation between O-2(.-) and Mn+, which are derived from the g(zz) values of the ESR spectra of the O-2(.-)-Mn+ complex.