As a rule, o-semiquinones decay through disproportionation leading to equimolar amounts of catechol and o-quinone products. However, the o-semiquinone 1S generated by pulse radiolysis oxidation of the eumelanin precursor 5,6-dihydroxyindole (1) decays with second-order kinetics to generate broad visible chromophores that are incompatible with the predicted absorption of 5,6-indolequinone (1Q). Using an integrated chemical, pulse radiolytic and computational approach as well as deuterium labeling, we show herein that 1S and related 5,6-dihydroxyindole semiquinones decay mainly by a free radical coupling mechanism. This conclusion was supported by the inverse kinetic isotope effect observed with deuterated IS, the identification of unprecedented dihydrobiindole products by one-electron oxidation of 1, the good matching of simulated absorption profiles of free radical coupling products of IS with experimental spectra, and a detailed computational analysis of the kinetics and thermodynamics of the disproportionation equilibrium and free radical coupling of IS versus 1-1Q. coupling. These results disclose, to the best of our knowledge, the first example of free radical dimerization of o-semiquinones outcompeting the classic disproportionation-driven catechol-quinone coupling and suggest that this hitherto unrecognized process may be of broader relevance than previously believed.