Interchange of complex formation and electron-transfer reactions between halide anions and p-benzoquinones were established via UV-vis spectral and X-ray structural measurements and computational analysis. Solution-phase interaction of the p-benzoquinone acceptors with Cl-, Br-, or I- donors led to the formation of anion-pi- complexes showing strong absorption bands in the UV-vis range. Formation constants and calculated interaction energies of these complexes increased, and donor/acceptor separations decreased with increasing reduction potentials of p-benzoquinones. Mulliken correlation and NBO analysis indicated a charge transfer nature of these anion-pi associates. Most notably, the increase of the acceptor strength led to a transition between the formation of the persistent anion-a complexes and electron-transfer reactions. Thermodynamic analysis accounted for the experimental observations of anion radicals and trihalide anions in solutions of p-benzoquinones with iodide or (for the strongest acceptor) bromide donors. Kinetics of these processes indicated that anion-pi complexes represent critical intermediates of the redox reactions. In contrast to Cl-, Br-, or I- anions, interaction of p-benzoquinones with F- anions led to the formation of sigma-complexes, and the appearance of anion radicals in such systems was related to the follow-up reactions of these complexes.