Reaction of [Ni(CH3CN)6][BF4]2 with [{(5,7-dimethyl-1,8-naphthyridin-2-yl)amino}carbonyl]ferrocene (L) in acetonitrile affords [NiII2(μ-F)2(L) 4][BF4]2 (1). X-ray structure reveals a fluoro-bridged Ni2F2 core with each Ni additionally coordinated to four N atoms from the two chelating ligands. The molecular mass signal is observed at m/z (z = 2) 848 in the ESI-MS. It is believed that the bimetallic activation of BF4-, followed by the trifluoroborane exclusion aided by the ligand L, results in the formation of (1). The NH⋯F interactions play an important role in the formation and stabilization of compound (1).