The mechanisms of the dearomative diborylation of pyrazines were investigated via a combination of density functional theory (DFT) calculations and experimental studies. DFT calculations revealed that a non-radical mechanism involving two successive [3,3]-σ-rearrangement-type processes is responsible for the diborylation of pyrazine with bis(pinacolato)diboron (B₂pin₂). However, this non-radical process is highly unfavorable for the diborylation reaction of sterically hindered pyrazine (2,3-dimethylpyrazine). For the diboration reaction of 2,3-dimethylpyrazine with B₂pin₂ in the presence of 2,6-dichloro-4,4′-bipyridine as the catalyst, 4,4′-bipyridine-mediated radical pathway proceeding through a B–B homolytic cleavage/boryl radical addition is preferred. Control experiments combined with kinetic studies provided supportive evidence for the proposed mechanism.