The hydroxo complex [NBu₄]₂[Ni₂(C₆F₅)₄(µ– OH)₂] reacts with H₂S or a thiol at room temperature in methanol to give the binuclear complexes [NBu₄]₂[Ni₂(C₆F₅)₄(µ– SR)₂](R = H, Me, Et, Prⁱ, Ph or C₆H₄Me-p). The trinuclear complex [NBu₄]₂[Ni₃(C₆F₅)₄(µ– SEt)₄] has been obtained by reaction of an excess of EtSH with the same hydroxo complex in refluxing methanol. The µ–azolato-µ-thiolato complexes [NBu₄]₂[Ni₂(C₆F₅)₄(µ– L)(µ– SR)](HL = pyrazole or 1,2,4-triazole; R = H, Ph or C₆H₄Me-p) can be prepared either by treating the µ-hydroxo–µ-azolato complexes [NBu₄]₂[Ni₂(C₆F₅)₄(µ– OH)(µ– L)] with H₂S or a thiol (1:1 molar ratio) or [NBu₄]₂[Ni₂(C₆F₅)₄(µ– OH)₂] with the corresponding thiol and azole (1:1:1 molar ratio). Analytical (C, H, N, S), conductance and spectrroscopic (IR, ¹H and ¹⁹F NMR) data have been used for structural assignments. An X-ray crystal structure determination of [NBu₄]₂[Ni₃(C₆F₅)₄(µ– SEt)₄] has established the trinuclear nature of the anion. The structure has been solved and refined to R= 0.052 and R′= 0.062 based on 3398 observed reflections. The Ni atoms are four-co-ordinated and show approximate square-planar arrangements. The bridge conformation could be determined by S ⋯ S repulsions.