The title compound, C(7)H(7)N·B(C(6)F(5))(3)·C(6)H(14), was obtained by the stoichiometric reaction of 2-vinyl-pyridine and tris-(penta-fluoro-phen-yl)borane in toluene. The formed adduct exhibits a restricted rotation along the B-N bond resulting in an asymmetry, which can be also observed in the (19)F NMR spectra. The B-N distance is equivalent to the distances found for 2-methyl-pyridine and 2-ethyl-pyridine B(C(6)F(5))(3) adducts. For the final refinement, the contributions of disordered solvent mol-ecules were removed from the diffraction data with SQUEEZE in PLATON [van der Sluis & Spek (1990). Acta Cryst. A46, 194-201; Spek (2009). Acta Cryst. D65, 148-155].