Carbon disulfide is cleaved by n‐propyldiphenylphosphine and nickel(II) bromide in a one‐step process, to form two unprecedented complexes: orange, [Ni(S2C2(PnPrPh2)2)Br(PnPrPh2)]Br⋅CS2 (1) and purple [Ni{η2‐SC(PnPrPh2)2}Br(PnPrPh2)]Br⋅0.5CS2 (2). Orange (1) contains a dithiolene‐related ligand that results from carbon–carbon bond formation, while purple (2) contains a remarkable ligand in which two n‐propyldiphenylphosphine molecules have added to a carbon atom of a CS unit that is coordinated to nickel. Carbon disulfide is cleaved by n‐propyldiphenyl‐phosphine in conjunction with nickel(II) bromide in a one‐step process, to form two unprecedented complexes: orange, [Ni(S2C2(PnPrPh2)2)Br(PnPrPh2)]Br⋅CS2 and purple [Ni{η2‐SC(PnPrPh2)2}Br(PnPrPh2)]Br⋅CS2.