An (N-heterocyclic carbene)nickel(I) hexamethyldisilazide deprotonates neopentanol (NpOH) to form the corresponding nickel(I) neopentoxide, which crystallizes as an alkoxide-bridged dimer. Reaction of the dimer with one equivalent of tert-butyldimethylsilyl trifluoromethanesulfonate gives an alkoxide-bridged dinickel(I) complex bridged by the CF3SO3 (OTf) anion. In both [LNiONp]2 and [(LNi)2(μ-ONp)(μ-OTf)], Ni•••Ni distances are consistent with the absence of metal–metal bonding, and Evans NMR data are consistent with the S = 1 spin state. Treatment of the dimer with two equivalents of silyl triflate results instead in complete abstraction of alkoxide. Addition of diethyl ether forms the monomeric d9 complex LNi(OEt2)OTf.