Homoleptic complexes adopting octahedral coordination modes are usually less active in catalysis due to the saturated coordination around metal centers that prevents substrate activation in a catalytic event. In this work, we demonstrated that a homoleptic octahedral cobalt complex (1) of 4'-pyridyl-2,2';6',2''-terpyridine that experienced monoprotonation at the non-coordinating pyridyl moiety upon crystallization could serve as a highly efficient precatalyst for the hydroboration of styrene derivatives with Markovnikov selectivity. The solid-state structure of this precatalyst along with relevant homoleptic CoII and FeII complexes has been characterized by X-ray crystallography. In the solid state, 1 features one-dimensional hydrogen-bonded chains that are further stacked by interchain π⋯π interactions. The newly synthesized complexes (1-3) along with several known analogues (4-6) were examined as precatalysts for the hydroboration of alkenes. The best-performing system, 1/KOtBu was found to promote Markovnikov hydroboration of substituted styrenes with high turnover frequencies (TOFs) up to ∼47 000 h-1, comparable to the most efficient polymeric catalyst [Co(pytpy)Cl2]n reported to date. Although some limitations in substrate scope as well as functional group tolerance exist, the catalyst shows good promise for several relevant hydrofunctionaliation reactions.