The reaction of [(η⁵-R₂PC₅H₄)₂Co][PF₆] with (Me₂S)AuCl (1:2) resulted in {[(η⁵-R₂PC₅H₄)₂Co](AuCl)₂}[PF₆] (R = Ph, Cy, or ⁱ Pr). With a 1:1 ratio of [(η⁵-R₂PC₅H₄)Co(η⁵-C₅H₅)][PF₆] to (Me₂S)AuCl, yellow crystalline {[(η⁵-R₂PC₅H₄)Co(η⁵-C₅H₅)](AuCl)}[PF₆] was produced. The reaction of {[(η⁵-Cy₂PC₅H₄)Co(η⁵-C₅H₅)](AuCl)}[PF₆] with phenyl acetylene gave {[(η⁵-Cy₂PC₅H₄)Co(η⁵-C₅H₅)][Au(C≡C–Ph)]}[PF₆], while the reaction of {[(η⁵-Cy₂PC₅H₄)₂Co](AuCl)₂}[PF₆] with phenyl acetylene produced the unusual ionic complex {[(η⁵-Cy₂PC₅H₄)₂Co][Au(C≡C–Ph)]₂}[Au(C≡C–Ph)₂]. The structure of this complex has been characterized by X-ray crystallography, and a possible pathway for its formation is suggested.